Parsimonious Topology Based on Frank-Kasper Polyhedra in Metal–Organic FrameworksClick to copy article linkArticle link copied!
- Soochan LeeSoochan LeeDepartment of Chemistry, Ulsan National Institute of Science and Technology, Ulsan 44919, Republic of KoreaMore by Soochan Lee
- Sungmin LeeSungmin LeeDepartment of Chemistry, Ulsan National Institute of Science and Technology, Ulsan 44919, Republic of KoreaMore by Sungmin Lee
- Yuna KwakYuna KwakDepartment of Chemistry, Ulsan National Institute of Science and Technology, Ulsan 44919, Republic of KoreaMore by Yuna Kwak
- Masood YousafMasood YousafCenter for Multidimensional Carbon Materials, Institute for Basic Science, Ulsan 44919, Republic of KoreaMore by Masood Yousaf
- Eunchan ChoEunchan ChoDepartment of Chemistry, Ulsan National Institute of Science and Technology, Ulsan 44919, Republic of KoreaMore by Eunchan Cho
- Hoi Ri MoonHoi Ri MoonDepartment of Chemistry and Nanoscience, Ewha Womans University, Seoul 03760, Republic of KoreaMore by Hoi Ri Moon
- Sung June Cho*Sung June Cho*Email: [email protected]Department of Chemical Engineering, Chonnam National University, Gwangju 61186, Republic of KoreaMore by Sung June Cho
- Noejung Park*Noejung Park*Email: [email protected]Center for Multidimensional Carbon Materials, Institute for Basic Science, Ulsan 44919, Republic of KoreaDepartment of Physics, Ulsan National Institute of Science and Technology, Ulsan 44919, Republic of KoreaMore by Noejung Park
- Wonyoung Choe*Wonyoung Choe*Email: [email protected]Department of Chemistry, Ulsan National Institute of Science and Technology, Ulsan 44919, Republic of KoreaGraduate School of Carbon Neutrality, Ulsan National Institute of Science and Technology, Ulsan 44919, Republic of KoreaGraduate School of Artificial Intelligence, Ulsan National Institute of Science and Technology, Ulsan 44919, Republic of KoreaMore by Wonyoung Choe
Abstract
A new topology previously unknown in metal–organic frameworks (MOFs) provides an important clue to uncovering a new series of polyhedral MOFs. We report a novel MOF crystallized in a parsimonious mep topology based on Frank–Kasper (FK) polyhedra. The distribution of angles in a tetrahedral arrangement (T-O-T) is crucial for the formation of FK polyhedra in mep topology. This finding led us to investigate the T-O-T angle distribution in related zeolites and zeolitic imidazolate frameworks (ZIFs). Unlike zeolites, it is extremely difficult to achieve high T-O-T angles in ZIFs, which prevents the formation of some FK topologies. Density functional theory (DFT) total energy calculations support a correlation between T-O-T angles and the feasibility of new tetrahedron-based FK frameworks. This result may lead to innovative ways of accessing new cellular topologies by simple chemical tweaking of T-O-T angles.
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Introduction
Results and Discussion
structure type | dual topology | space group | tiling [512]:[51262]:[51263]:[51264] |
---|---|---|---|
Cr3Si | mep | Pm3̅n | 1:3:0:0 |
MgCu2 | mtn | Fd3̅m | 2:0:0:1 |
MgZn2 | mgz-x-d | P63/mmc | 2:0:0:1 |
Zr4Al3 | zra-d | P6/mmm | 3:2:2:0 |
Cr46Fe54 | sig | P42/mnm | 5:8:2:0 |
W6Fe7 | mur | R3̅m | 7:2:2:2 |
K7Cs6 | muh | P63/mmc | 7:2:2:2 |
Mg32(Zn, Al)49 | tei | Im3̅ | 49:6:6:20 |
Conclusions
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacsau.4c00285.
Materials and general procedures; detailed experimental and computational methods; characterization of FKMOFs including 1H NMR, PXRD, and SCXRD; measurements of structural information (PDF)
FKMOF-1 (CIF)
FKMOF-2 (CIF)
Models for hypothetical FKMOFs (ZIP)
CCDC 1847765 (FKMOF-1) and 1487207 (FKMOF-2) contains the supporting crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre,12 Union Road, Cambridge CB2 1EZ, U.K.; fax: + 44 1223 336033.
Terms & Conditions
Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.
Acknowledgments
This work was financially supported by National Research Foundation of Korea (NRF-2021M3I3A1084909, RS-2023-00279793, RS-2023-00218799 and RS-2023-00208825). M.Y. acknowledges the financial support from Institute for Basic Science (IBS-R019-D1). X-ray diffraction experiments using synchrotron radiation were performed at the PAL in Korea for beamline use (2014-third-2D-024 and 2018-first-2D-030).
References
This article references 79 other publications.
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- 5Lu, W.; Wei, Z.; Gu, Z.-Y.; Liu, T.-F.; Park, J.; Park, J.; Tian, J.; Zhang, M.; Zhang, Q.; Gentle Iii, T.; Bosch, M.; Zhou, H.-C. Tuning the Structure and Function of Metal–Organic Frameworks via Linker Design. Chem. Soc. Rev. 2014, 43 (16), 5561– 5593, DOI: 10.1039/C4CS00003JGoogle Scholar5https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXht1Slu7jK&md5=322785c0256204742e3e95e5d2d49914Tuning the structure and function of metal-organic frameworks via linker designLu, Weigang; Wei, Zhangwen; Gu, Zhi-Yuan; Liu, Tian-Fu; Park, Jinhee; Park, Jihye; Tian, Jian; Zhang, Muwei; Zhang, Qiang; Gentle III, Thomas; Bosch, Mathieu; Zhou, Hong-CaiChemical Society Reviews (2014), 43 (16), 5561-5593CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)A review. Metal-org. frameworks (MOFs) are constructed from metal ions/clusters coordinated by org. linkers (or bridging-ligands). The hallmark of MOFs is their permanent porosity, which is frequently found in MOFs constructed from metal-clusters. These clusters are often formed in situ, whereas the linkers are generally pre-formed. The geometry and connectivity of a linker dictate the structure of the resulting MOF. Adjustments of linker geometry, length, ratio, and functional-group can tune the size, shape, and internal surface property of a MOF for a targeted application. In this crit. review, the authors highlight advances in MOF synthesis focusing on linker design. Examples of building MOFs to reach unique properties, such as unprecedented surface area, pore aperture, mol. recognition, stability, and catalysis, through linker design are described. Further search for application-oriented MOFs through judicious selection of metal clusters and org. linkers is desirable. In this review, linkers are categorized as ditopic (Section 1), tritopic (Section 2), tetratopic (Section 3), hexatopic (Section 4), octatopic (Section 5), mixed (Section 6), desymmetrized (Section 7), metallo (Section 8), and N-heterocyclic linkers (Section 9).
- 6O’Keeffe, M.; Peskov, M. A.; Ramsden, S. J.; Yaghi, O. M. The Reticular Chemistry Structure Resource (RCSR) Database of, and Symbols for, Crystal Nets. Acc. Chem. Res. 2008, 41 (12), 1782– 1789, DOI: 10.1021/ar800124uGoogle Scholar6https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXht1SgsrjF&md5=392c624f403dd8457460a7649aa496f3The Reticular Chemistry Structure Resource (RCSR) database of, and symbols for, crystal netsO'Keeffe, Michael; Peskov, Maxim A.; Ramsden, Stuart J.; Yaghi, Omar M.Accounts of Chemical Research (2008), 41 (12), 1782-1789CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)During the past decade, interest has grown tremendously in the design and synthesis of cryst. materials constructed from mol. clusters linked by extended groups of atoms. Most notable are metal-org. frameworks (MOFs), in which polyat. inorg. metal-contg. clusters are joined by polytopic linkers. (Although these materials are sometimes referred to as coordination polymers, we prefer to differentiate them, because MOFs are based on strong linkages that yield robust frameworks.) The realization that MOFs could be designed and synthesized in a rational way from mol. building blocks led to the emergence of a discipline that we call reticular chem.MOFs can be represented as a special kind of graph called a periodic net. Such descriptions date back to the earliest crystallog. studies but have become much more common recently because thousands of new structures and hundreds of underlying nets have been reported. In the simplest cases (e.g., the structure of diamond), the atoms in the crystal become the vertices of the net, and bonds are the links (edges) that connect them. In the case of MOFs, polyat. groups act as the vertices and edges of the net.Because of the explosive growth in this area, a need has arisen for a universal system of nomenclature, classification, identification, and retrieval of these topol. structures. We have developed a system of symbols for the identification of three periodic nets of interest, and this system is now in wide use. In this Account, we explain the underlying methodol. of assigning symbols and describe the Reticular Chem. Structure Resource (RCSR), in which about 1600 such nets are collected and illustrated in a database that can be searched by symbol, name, keywords, and attributes. The resource also contains searchable data for polyhedra and layers.The database entries come from systematic enumerations or from known chem. compds. or both. In the latter case, refs. to occurrences are provided. We describe some crystallog., topol., and other attributes of nets and explain how they are reported in the database. We also describe how the database can be used as a tool for the design and structural anal. of new materials. Assocd. with each net is a natural tiling, which is a natural partition of space into space-filling tiles. The database allows export of data that can be used to analyze and illustrate such tilings.
- 7O’Keeffe, M. Design of MOFs and Intellectual Content in Reticular Chemistry: A Personal View. Chem. Soc. Rev. 2009, 38 (5), 1215– 1217, DOI: 10.1039/b802802hGoogle Scholar7https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXkvVamu78%253D&md5=3811ee3f78991faa0cd9e0524b6aee3cDesign of MOFs and intellectual content in reticular chemistry: a personal viewO'Keeffe, MichaelChemical Society Reviews (2009), 38 (5), 1215-1217CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)A review. This article gives a personal perspective on the ideas leading to the development of reticular chem. The feasibility of achieving targeted materials with predetd. metrics and functionality by designed synthesis is defended.
- 8Tranchemontagne, D. J.; Mendoza-Cortés, J. L.; O’Keeffe, M.; Yaghi, O. M. Secondary Building Units, Nets and Bonding in the Chemistry of Metal–Organic Frameworks. Chem. Soc. Rev. 2009, 38 (5), 1257– 1283, DOI: 10.1039/b817735jGoogle Scholar8https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXkvValsr8%253D&md5=3e03c5e2c057b36eb590c1904aa5e5a1Secondary building units, nets and bonding in the chemistry of metal-organic frameworksTranchemontagne, David J.; Mendoza-Cortes, Jose L.; O'Keeffe, Michael; Yaghi, Omar M.Chemical Society Reviews (2009), 38 (5), 1257-1283CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)This crit. review presents a comprehensive study of transition-metal carboxylate clusters which may serve as secondary building units (SBUs) towards construction and synthesis of metal-org. frameworks (MOFs). We describe the geometries of 131 SBUs, their connectivity and compn. This contribution presents a comprehensive list of the wide variety of transition-metal carboxylate clusters which may serve as secondary building units (SBUs) in the construction and synthesis of metal-org. frameworks. The SBUs discussed here were obtained from a search of mols. and extended structures archived in the Cambridge Structure Database (CSD, version 5.28, Jan. 2007) which included only crystals contg. metal carboxylate linkages (241 refs.).
- 9Jiang, H.; Alezi, D.; Eddaoudi, M. E. A reticular chemistry guide for the design of periodic solids. Nat. Rev. Mater. 2021, 6 (6), 466– 487, DOI: 10.1038/s41578-021-00287-yGoogle Scholar9https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhsFegurvL&md5=6e9a10dfa101cc33649d49856f859d01Review on reticular chemistry guide for the design of periodic solidsJiang, Hao; Alezi, Dalal; Eddaoudi, MohamedNature Reviews Materials (2021), 6 (6), 466-487CODEN: NRMADL; ISSN:2058-8437. (Nature Portfolio)A review. Abstr.: Reticular chem. - the linking of well-defined mol. building blocks by strong bonds into cryst. extended frameworks - has enabled the synthesis of diverse metal-org. frameworks (MOFs) and covalent org. frameworks, in which the pore shape, size and functionality can be tailored towards specific applications. Structural design methodologies are based on three main requisites: building blocks, targeted nets and isoreticular chem. In this Review, we highlight the well-developed and cutting-edge methodologies in reticular chem. for the structural design and discovery of periodic solids. We illustrate the diversity of building blocks and delineate the suitable blueprint nets - namely, edge-transitive nets - for the design of MOFs. These edge-transitive nets are classified into three categories to help rationalize existing MOFs and to provide guidelines for the design of new structures. Two emerging topol. concepts, namely, the merged-net approach and net-coded building units, are highlighted for their potential in synthesizing intricate or multi-component MOFs. We also consider isoreticular design strategies for the modification, expansion and contraction of building blocks, and identify challenges and opportunities in the assembly of increasingly intricate frameworks.
- 10Guillerm, V.; Kim, D.; Eubank, J. F.; Luebke, R.; Liu, X.; Adil, K.; Lah, M. S.; Eddaoudi, M. A Supermolecular Building Approach for the Design and Construction of Metal–Organic Frameworks. Chem. Soc. Rev. 2014, 43 (16), 6141– 6172, DOI: 10.1039/C4CS00135DGoogle Scholar10https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhtFehsbvO&md5=97bf12cb969bfc7f409f5f06facd593bA supermolecular building approach for the design and construction of metal-organic frameworksGuillerm, Vincent; Kim, Dongwook; Eubank, Jarrod F.; Luebke, Ryan; Liu, Xinfang; Adil, Karim; Lah, Myoung Soo; Eddaoudi, MohamedChemical Society Reviews (2014), 43 (16), 6141-6172CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)A review. In this review, the authors describe two recently implemented conceptual approaches facilitating the design and deliberate construction of metal-org. frameworks (MOFs), supermol. building block (SBB) and supermol. building layer (SBL) approaches. The authors' main objective is to offer an appropriate means to assist/aid chemists and material designers alike to rationally construct desired functional MOF materials, made-to-order MOFs. The authors introduce the concept of net-coded building units (net-cBUs), where precise embedded geometrical information codes uniquely and matchlessly a selected net, as a compelling route for the rational design of MOFs. This concept is based on employing pre-selected 0-periodic metal-org. polyhedra or 2-periodic metal-org. layers, SBBs or SBLs, resp., as a pathway to access the requisite net-cBUs. In this review, inspired by the authors' success with the original rht-MOF, the authors extrapolated the authors' strategy to other known MOFs via their deconstruction into more elaborate building units (polyhedra or layers) to (i) elucidate the unique relation between edge-transitive polyhedra or layers and minimal edge-transitive 3-periodic nets, and (ii) illustrate the potential of the SBB and SBL approaches as a rational pathway for the design and construction of 3-periodic MOFs. Using this design strategy, the authors have also identified several new hypothetical MOFs which are synthetically targetable.
- 11Kim, D.; Liu, X.; Lah, M. S. Topology Analysis of Metal–Organic Frameworks Based on Metal–Organic Polyhedra as Secondary or Tertiary Building Units. Inorg. Chem. Front. 2015, 2 (4), 336– 360, DOI: 10.1039/C4QI00236AGoogle ScholarThere is no corresponding record for this reference.
- 12Khobotov-Bakishev, A.; Hernández-López, L.; von Baeckmann, C.; Albalad, J.; Carné-Sánchez, A.; Maspoch, D. Metal–Organic Polyhedra as Building Blocks for Porous Extended Networks. Adv. Sci. 2022, 9 (11), 2104753 DOI: 10.1002/advs.202104753Google ScholarThere is no corresponding record for this reference.
- 13Guillerm, V.; Eddaoudi, M. The Importance of Highly Connected Building Units in Reticular Chemistry: Thoughtful Design of Metal–Organic Frameworks. Acc. Chem. Res. 2021, 54 (17), 3298– 3312, DOI: 10.1021/acs.accounts.1c00214Google Scholar13https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhsVKrtL3K&md5=54b28aee95182a070397635423279566The Importance of Highly Connected Building Units in Reticular Chemistry: Thoughtful Design of Metal-Organic FrameworksGuillerm, Vincent; Eddaoudi, MohamedAccounts of Chemical Research (2021), 54 (17), 3298-3312CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)A review. The prediction of crystal structures assembled in three dimensions has been considered for a long time, simultaneously as a "chem. wasteland" and "a certain growth point of the chem. of the future". Less than 30 years after Roald Hoffmann's statement, we can categorically affirm that the raise of reticular chem. and introduction of metal-org. frameworks (MOFs) significantly tackled this tridimensional assembly issue. MOFs result from the assembly of org. polytopic org. ligands bridging metal nodes, clusters, chains or layers together into, mostly, 3-periodic open frameworks. They can exhibit extremely high porosity, offer great potential as revolutionary catalysts, drug carrier systems, sensors, smart materials, and of course, sepn. agents. Overall, the progressive development of reticular chem. has been a game changer in materials chem. during the last 25 years. Such diverse properties often result not only from the selected org. and inorg. mol. building blocks (MBBs), but also on their distribution within the framework. Indeed, the size, shape of porous system, influence the overall properties, as well as the location of the active sites. Therefore, in the continuity of achieving the crystn. of 3-periodic structures, chemists and crystal engineers faced the next challenge, summarized by John Maddox, "it remains in general impossible to predict the structure of even the simplest crystallog. solids from knowledge of their chem. compn.". This is where rational design takes place. In this account, we detail three specific approaches developed by our group to facilitate the design and assembly of finely tuned MOFs. All are based on careful geometrical consideration and a deep study and understanding of the existing nets, topologies. We recognized highly connected nets, if possible edge-transitive, are ideal blueprints, as their no. is limited in contrast to nets with lower connectivity. Therefore, we embarked in taking advantage of existing highly connected MBBs, or in parallel, promoting their formation to meet our requirements. This is achieved by utilizing externally decorated metal-org. polyhedra as supermol. building blocks (SBBs), serving as a net-coding building unit, comprising the requisite connectivity and directional information coding for the chosen nets. The SBB approach allowed the synthesis of several families of SBB based MOFs, including fcu, rht, and gea-MOFs, that are detailed here. The second strategy is directly inherited from the success of the SBB approach. Seeking for highly connected building units, our group naturally expanded its research focus to nets that can be deconstructed into layers, pillared in various ways. In the supermol. building layer (SBL) approach, the layers have an almost infinite connectivity, and the framework backbone is fixed in two dimensions while the third is free for pillar expansion and functionalization. The cases of trigonal pillaring leading to rtl, eea and apo MOFs, as well as the quadrangular pillaring leading to a family of tbo-MOFs is discussed here, along with recent cases of highly connected pillars in pek and aea-MOFs. Finally, our experience with highly coordinated MBBs led us to develop a novel way to use them as secondary building units of lower connectivity and unlock the possibility of assembling a novel class of zeolite-like MOFs (ZMOFs). The case of the Zr-sod-ZMOFs designed through a cantellation strategy is described as a future leading direction of MOFs design.
- 14Li, P.; Vermeulen, N. A.; Malliakas, C. D.; Gómez-Gualdrón, D. A.; Howarth, A. J.; Mehdi, B. L.; Dohnalkova, A.; Browning, N. D.; O’Keeffe, M.; Farha, O. K. Bottom-up construction of a superstructure in a porous uranium-organic crystal. Science 2017, 356 (6338), 624– 627, DOI: 10.1126/science.aam7851Google Scholar14https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXnt1Chs78%253D&md5=ce8c4f6f63a111d50bcad772348d7c71Bottom-up construction of a superstructure in a porous uranium-organic crystalLi, Peng; Vermeulen, Nicolaas A.; Malliakas, Christos D.; Gomez-Gualdron, Diego A.; Howarth, Ashlee J.; Mehdi, B. Layla; Dohnalkova, Alice; Browning, Nigel D.; O'Keeffe, Michael; Farha, Omar K.Science (Washington, DC, United States) (2017), 356 (6338), 624-627CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Bottom-up construction of highly intricate structures from simple building blocks remains one of the most difficult challenges in chem. The authors report a structurally complex, mesoporous uranium-based metal-org. framework (MOF) made from simple starting components. The structure comprises 10 uranium nodes and seven tricarboxylate ligands (both crystallog. nonequivalent), resulting in a 173.3-Å cubic unit cell enclosing 816 uranium nodes and 816 org. linkers-the largest unit cell found to date for any nonbiol. material. The cuboctahedra organize into pentagonal and hexagonal prismatic secondary structures, which then form tetrahedral and diamond quaternary topologies with unprecedented complexity. This packing gave colossal icosidodecahedral and rectified hexakaidecahedral cavities with internal diams. of 5.0 nm and 6.2 nm, resp.-ultimately giving rise to the lowest-d. MOF reported to date.
- 15Barsukova, M.; Sapianik, A.; Guillerm, V.; Shkurenko, A.; Shaikh, A. C.; Parvatkar, P.; Bhatt, P. M.; Bonneau, M.; Alhaji, A.; Shekhah, O.; Balestra, S. R. G.; Semino, R.; Maurin, G.; Eddaoudi, M. Face-directed assembly of tailored isoreticular MOFs using centring structure-directing agents. Nat. Synth. 2024, 3 (1), 33– 46, DOI: 10.1038/s44160-023-00401-8Google ScholarThere is no corresponding record for this reference.
- 16O’Keeffe, M. Crystal Structures as Periodic Foams and Vice Versa. In Foams and Emulsions; Sadoc, J. F.; Rivier, N., Eds.; Springer Netherlands: Dordrecht, 1999; pp; pp 403– 422.Google ScholarThere is no corresponding record for this reference.
- 17Frank, F. C.; Kasper, J. S. Complex Alloy Structures Regarded as Sphere Packings. I. Definitions and Basic Principles. Acta Crystallogr. 1958, 11 (3), 184– 190, DOI: 10.1107/S0365110X58000487Google Scholar17https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaG1cXkvVCjsA%253D%253D&md5=7610405316848e64c343a39d887ba2d6Complex alloy structures regarded as sphere packings. I. Definitions and basic principlesFrank, F. C.; Kasper, J. S.Acta Crystallographica (1958), 11 (), 184-90CODEN: ACCRA9; ISSN:0365-110X.Complex alloy structures, particularly those of transition metals, are considered as detd. by the geometrical requirements for sphere packing. A characteristic of the class of structures discussed is that tetrahedral groupings of atoms occur everywhere in the structure, that is co.ovrddot.ordination polyhedra have only triangular faces. The topological and geometrical properties of such polyhedra are examd., and rules and theorems regarding them are deduced. Justification is given for the prominence of 4 such polyhedra (for co.ovrddot.ordination nos. of 12, 14, 15, and 16) in actual structures. General principles regarding the combination of these polyhedra into full structures are deduced, and necessary definitions are given for terms that facilitate the detailed discussion of this class of structures.
- 18Frank, F. C.; Kasper, J. S. Complex Alloy Structures Regarded as Sphere Packings. II. Analysis and Classification of Representative Structures. Acta Crystallogr. 1959, 12 (7), 483– 499, DOI: 10.1107/S0365110X59001499Google Scholar18https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaG1MXhtV2isbw%253D&md5=467d707d352d379c9ff427335c84d67aComplex alloy structures regarded as sphere packings. II. Analysis and classification of representative structuresFrank, F. C.; Kasper, J. S.Acta Crystallographica (1959), 12 (), 483-99CODEN: ACCRA9; ISSN:0365-110X.cf. C.A. 52, 8670d. The general principles and properties deduced previously for the class of alloy structures with triangulated co.ovrddot.ordination polyhedra, are applied in an analysis and classification of representative structures. In the main, the analysis deals with the nature of layers and how they can be stacked and with the nature of the major skeletons. Many hypothetical structures resulting from the analysis are listed, and procedures are given for predicting other structure types. The relation between alloy structures and inert gas hydrates is discussed.
- 19Bonneau, C.; O’Keeffe, M. Intermetallic Crystal Structures as Foams. Beyond Frank–Kasper. Inorg. Chem. 2015, 54 (3), 808– 814, DOI: 10.1021/ic5017966Google ScholarThere is no corresponding record for this reference.
- 20Sikirić, M. D.; Delgado-Friedrichs, O.; Deza, M. Space Fullerenes: A Computer Search for New Frank–Kasper Structures. Acta Crystallogr., Sect. A: Found. Crystallogr. 2010, 66 (5), 602– 615, DOI: 10.1107/S0108767310022932Google ScholarThere is no corresponding record for this reference.
- 21Kamb, B. A Clathrate Crystalline Form of Silica. Science 1965, 148 (3667), 232– 234, DOI: 10.1126/science.148.3667.232Google ScholarThere is no corresponding record for this reference.
- 22Gies, H. Studies on Clathrasils. III.*: Crystal Structure of Melanophlogite, a Natural Clathrate Compound of Silica**. Z. Kristallogr. - Cryst. Mater. 1983, 164 (3–4), 247– 257, DOI: 10.1524/zkri.1983.164.3-4.247Google ScholarThere is no corresponding record for this reference.
- 23Momma, K.; Ikeda, T.; Nishikubo, K.; Takahashi, N.; Honma, C.; Takada, M.; Furukawa, Y.; Nagase, T.; Kudoh, Y. New Silica Clathrate Minerals That Are Isostructural with Natural Gas Hydrates. Nat. Commun. 2011, 2 (1), 196 DOI: 10.1038/ncomms1196Google Scholar23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC3M7pslyluw%253D%253D&md5=5343e64269b2353d65f81786b5ed5834New silica clathrate minerals that are isostructural with natural gas hydratesMomma Koichi; Ikeda Takuji; Nishikubo Katsumi; Takahashi Naoki; Honma Chibune; Takada Masayuki; Furukawa Yoshihiro; Nagase Toshiro; Kudoh YasuhiroNature communications (2011), 2 (), 196 ISSN:.Silica clathrate compounds (clathrasils) and clathrate hydrates are structurally analogous because both materials have framework structures with cage-like voids occupied by guest species. The following three structural types of clathrate hydrates are recognized in nature: cubic structure I (sI); cubic structure II (sII); and hexagonal structure H (sH). In contrast, only one naturally occurring silica clathrate mineral, melanophlogite (sI-type framework), has been found to date. Here, we report the discovery of two new silica clathrate minerals that are isostructural with sII and sH hydrates and contain hydrocarbon gases. Geological and mineralogical observations show that these silica clathrate minerals are traces of low-temperature hydrothermal systems at convergent plate margins, which are the sources of thermogenic natural gas hydrates. Given the widespread occurrence of submarine hydrocarbon seeps, silica clathrate minerals are likely to be found in a wide range of marine sediments.
- 24Sloan, E. D. Fundamental Principles and Applications of Natural Gas Hydrates. Nature 2003, 426 (6964), 353– 359, DOI: 10.1038/nature02135Google Scholar24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXptVOitLk%253D&md5=5009d19b104518ee0fd248dbbf2a72a7Fundamental principles and applications of natural gas hydratesSloan, E. DendyNature (London, United Kingdom) (2003), 426 (6964), 353-363CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)Natural gas hydrates are solid, non-stoichiometric compds. of small gas mols. and water. They form when the constituents come into contact at low temp. and high pressure. The phys. properties of these compds., most notably that they are non-flowing cryst. solids that are denser than typical fluid hydrocarbons and that the gas mols. they contain are effectively compressed, give rise to numerous applications in the broad areas of energy and climate effects. In particular, they have an important bearing on flow assurance and safety issues in oil and gas pipelines, they offer a largely unexploited means of energy recovery and transportation, and they could play a significant role in past and future climate change.
- 25Kirchner, M. T.; Boese, R.; Billups, W. E.; Norman, L. R. Gas Hydrate Single-Crystal Structure Analyses. J. Am. Chem. Soc. 2004, 126 (30), 9407– 9412, DOI: 10.1021/ja049247cGoogle Scholar25https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXlsFKrsrc%253D&md5=a7b01b53e54422b882ee9a87a2d2236bGas Hydrate Single-Crystal Structure AnalysesKirchner, Michael T.; Boese, Roland; Billups, W. Edward; Norman, Lewis R.Journal of the American Chemical Society (2004), 126 (30), 9407-9412CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)The 1st single-crystal diffraction studies on methane, propane, methane/propane, and adamantane gas hydrates SI, SII , and SH were performed. To circumvent the problem of very slow crystal growth, a novel technique of in situ cocrystn. of gases and liqs. resulting in oligocryst. material in a capillary was developed. With special data treatment, termed oligo diffractometry, structural data of the gas hydrates of methane, acetylene, propane, a propane/ethanol/methane-mixt. and an adamantane/methane-mixt. were obtained. Cell parameters are in accord with reported values. Host network and guest are subject to extensive disorder, reducing the reliability of structural information. Most cages are fully occupied by a guest mol. with the exception of the dodecahedral cage in the acetylene hydrate which is only filled to 60%. For adamantane in the icosahedral cage a disordered model is proposed.
- 26Pouchard, M.; Cros, C. The Early Development of Inorganic Clathrates. In The Physics and Chemistry of Inorganic Clathrates; Nolas, G. S., Ed.; Springer Netherlands: Dordrecht, 2014; Vol. 199, pp 1– 33.Google ScholarThere is no corresponding record for this reference.
- 27Kasper, J. S.; Hagenmuller, P.; Pouchard, M.; Cros, C. Clathrate Structure of Silicon Na8 Si46 and Nax Si136 (x < 11). Science 1965, 150 (3704), 1713– 1714, DOI: 10.1126/science.150.3704.1713Google ScholarThere is no corresponding record for this reference.
- 28Aydemir, U.; Akselrud, L.; Carrillo-Cabrera, W.; Candolfi, C.; Oeschler, N.; Baitinger, M.; Steglich, F.; Grin, Y. BaGe 5 : A New Type of Intermetallic Clathrate. J. Am. Chem. Soc. 2010, 132 (32), 10984– 10985, DOI: 10.1021/ja104197cGoogle Scholar28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXpsVWltb8%253D&md5=3ee7068e3514453e86b2a64b581baed3BaGe5: A New Type of Intermetallic ClathrateAydemir, Umut; Akselrud, Lev; Carrillo-Cabrera, Wilder; Candolfi, Christophe; Oeschler, Niels; Baitinger, Michael; Steglich, Frank; Grin, YuriJournal of the American Chemical Society (2010), 132 (32), 10984-10985CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)BaGe5 constitutes a new type of intermetallic clathrate obtained by decompn. of clathrate-I Ba8Ge43.box.3 at low temps. The crystal structure consists of characteristic layers interconnected by covalent bonds. BaGe5 is a semiconducting Zintl phase.
- 29He, Y.; Sui, F.; Kauzlarich, S. M.; Galli, G. Si-Based Earth Abundant Clathrates for Solar Energy Conversion. Energy Environ. Sci. 2014, 7 (8), 2598– 2602, DOI: 10.1039/C4EE00256CGoogle Scholar29https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXht1CltLzJ&md5=c0a832abf8e91dd06e15a036f09154d2Si-based Earth abundant clathrates for solar energy conversionHe, Yuping; Sui, Fan; Kauzlarich, Susan M.; Galli, GiuliaEnergy & Environmental Science (2014), 7 (8), 2598-2602CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)We synthesized a Si-based clathrate, composed entirely of Earth abundant elements, and using ab initio calcns. and spectroscopic and Hall mobility measurement showed that it is a promising material for solar energy conversion. We found that the type-I clathrate K8Al8Si38 exhibits a quasi-direct band gap of ∼1.0 eV, which may be tuned to span the IR and visible range by strain engineering. We also found that upon light absorption, excited electron and hole states are spatially sepd. in the material, with low probability of charge recombination. Finally, we computed and measured electron and hole mobilities and obtained values much superior to those of a-Si and approx. 6 to 10 and 10 to 13 time smaller than those of cryst. Si.
- 30Sui, F.; He, H.; Bobev, S.; Zhao, J.; Osterloh, F. E.; Kauzlarich, S. M. Synthesis, Structure, Thermoelectric Properties, and Band Gaps of Alkali Metal Containing Type I Clathrates: A 8 Ga 8 Si 38 (A = K, Rb, Cs) and K 8 Al 8 Si 38. Chem. Mater. 2015, 27 (8), 2812– 2820, DOI: 10.1021/cm504436vGoogle ScholarThere is no corresponding record for this reference.
- 31Luo, M.-B.; Chen, L.-J.; Huang, S.-L.; Zhou, X.; Chen, E.-X.; Lin, Q. Zeolite Analogues Based on Oxysulfidometalate Supertetrahedral Clusters via Coulombic Interactions. Inorg. Chem. Front. 2023, 10, 3224– 3229, DOI: 10.1039/D3QI00360DGoogle ScholarThere is no corresponding record for this reference.
- 32Klarreich, E. G. Foams and Honeycombs: For centuries, the precise architecture of soap foams has been a source of wonder to children and a challenge to mathematicians. Am. Sci. 2000, 88, 152– 161Google ScholarThere is no corresponding record for this reference.
- 33Boomsma, K.; Poulikakos, D.; Ventikos, Y. Simulations of flow through open cell metal foams using an idealized periodic cell structures. Int. J. Heat Fluid Flow 2003, 24, 825– 834, DOI: 10.1016/j.ijheatfluidflow.2003.08.002Google ScholarThere is no corresponding record for this reference.
- 34Ball, P. Beijing Bubbles. Nature 2007, 448 (7151), 256, DOI: 10.1038/448256aGoogle ScholarThere is no corresponding record for this reference.
- 35Chen, Y.; Takeya, S.; Sum, A. K. Topological Dual and Extended Relations between Networks of Clathrate Hydrates and Frank-Kasper Phases. Nat. Commun. 2023, 14 (1), 596 DOI: 10.1038/s41467-023-36242-4Google ScholarThere is no corresponding record for this reference.
- 36Hudson, S. D.; Jung, H.-T.; Percec, V.; Cho, W.-D.; Johansson, G.; Ungar, G.; Balagurusamy, V. S. K. Direct Visualization of Individual Cylindrical and Spherical Supramolecular Dendrimers. Science 1997, 278 (5337), 449– 452, DOI: 10.1126/science.278.5337.449Google Scholar36https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2sXmslKjtrY%253D&md5=7c9bbc5ae7ff97c499aacea519edb208Direct visualization of individual cylindrical and spherical supramolecular dendrimersHudson, S. D.; Jung, H.-T.; Percec, V.; Cho, W.-D.; Johansson, G.; Ungar, G.; Balagurusamy, V. S. K.Science (Washington, D. C.) (1997), 278 (5337), 449-452CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Electron microscopy methods have been used to visualize individual spherical and cylindrical supramol. dendrimers, providing definitive confirmation of the structure suggested by previous x-ray diffraction anal. that assumed a micro-segregated model. These dendrimers are self-assembled self-organized, and aligned spontaneously and simultaneously in hexagonal columnar or cubic thermotropic liq.-crystal phases with high uniformity. Homeotropic and planar ordering of the hexagonal columnar liq. crystal was precisely controlled by a variety of surfaces. The stiffness of these cylinders was evaluated by examg. their planar texture and its defects.
- 37Percec, V.; Cho, W.-D.; Möller, M.; Prokhorova, S. A.; Ungar, G.; Yeardley, D. J. P. Design and Structural Analysis of the First Spherical Monodendron Self-Organizable in a Cubic Lattice. J. Am. Chem. Soc. 2000, 122 (17), 4249– 4250, DOI: 10.1021/ja9943400Google Scholar37https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3cXitlyquro%253D&md5=a1f806f7cf80dd67e5186c62783329a7Design and Structural Analysis of the First Spherical Monodendron Self-Organizable in a Cubic LatticePercec, Virgil; Cho, Wook-Dong; Moeller, Martin; Prokhorova, Svetlana A.; Ungar, Goran; Yeardley, Duncan J. P.Journal of the American Chemical Society (2000), 122 (17), 4249-4250CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)The design, synthesis (divergent approach with Me 3,4,5-trihydroxybenzoate), and structural anal. (by x-ray diffraction) of spherical functional monodendrons of the type (3,4-(3,4,5)n-1)12GnX (n (generation) = 1-5, and X = CH2OH, COOH, or CO2CH3) that self-organizes in a cubic Pm3n lattice is reported. The prepd. monodendrons were addnl. examd. by differential scanning calorimetry, thermal optical polarized microscopy, and scanning force microscopy. The lattice parameters, the diam. of supramol. or mol. dendritic sphere, the no. of monodendrons that self-assemble into a sphere, and the theor. molar mass of the monodendrons were detd.
- 38Ungar, G.; Liu, Y.; Zeng, X.; Percec, V.; Cho, W.-D. Giant Supramolecular Liquid Crystal Lattice. Science 2003, 299 (5610), 1208– 1211, DOI: 10.1126/science.1078849Google Scholar38https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXht12jtLc%253D&md5=8ca2656f954ef3d899050785d222e586Giant Supramolecular Liquid Crystal LatticeUngar, Goran; Liu, Yongsong; Zeng, Xiangbing; Percec, Virgil; Cho, Wook-DongScience (Washington, DC, United States) (2003), 299 (5610), 1208-1211CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Self-organized supramol. org. nanostructures have potential applications that include mol. electronics, photonics, and precursors for nanoporous catalysts. Accordingly, understanding how self-assembly is controlled by mol. architecture will enable the design of increasingly complex structures. The authors report a liq. crystal (LC) phase with a tetragonal three-dimensional unit cell contg. 30 globular supramol. dendrimers, each of which is self-assembled from 12 dendron (tree-like) mols., for the compds. described here. The present structure is one of the most complex LC phases yet discovered. A model explaining how spatial arrangement of self-assembled dendritic aggregates depends on mol. architecture and temp. is proposed.
- 39Percec, V.; Peterca, M.; Dulcey, A. E.; Imam, M. R.; Hudson, S. D.; Nummelin, S.; Adelman, P.; Heiney, P. A. Hollow Spherical Supramolecular Dendrimers. J. Am. Chem. Soc. 2008, 130 (39), 13079– 13094, DOI: 10.1021/ja8034703Google Scholar39https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXhtVOqtLvN&md5=0025780b59b8620d5999c23a572a4b71Hollow Spherical Supramolecular DendrimersPercec, Virgil; Peterca, Mihai; Dulcey, Andres E.; Imam, Mohammad R.; Hudson, Steven D.; Nummelin, Sami; Adelman, Peter; Heiney, Paul A.Journal of the American Chemical Society (2008), 130 (39), 13079-13094CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)The synthesis of a library contg. 12 conical dendrons that self-assemble into hollow spherical supramol. dendrimers is reported. The design principles for this library were accessed by development of a method that allows the identification of hollow spheres, followed by structural and retrostructural anal. of their Pm‾3n cubic lattice. The first hollow spherical supramol. dendrimer was made by replacing the tapered dendron, from the previously reported tapered dendritic dipeptide that self-assembled into helical pores, with its constitutional isomeric conical dendron. This strategy generated a conical dendritic dipeptide that self-assembled into a hollow spherical supramol. dendrimer that self-organizes in a Pm‾3n cubic lattice. Other examples of hollow spheres were assembled from conical dendrons without a dipeptide at their apex. These are conical dendrons originated from tapered dendrons contg. addnl. benzyl ether groups at their apex. The inner part of the hollow sphere assembled from the dipeptide resembles the path of a spherical helix or loxodrome and, therefore, is chiral. The spheres assembled from other conical dendrons are nonhelical, even when they contain stereocenters on the alkyl groups from their periphery. Functionalization of the apex of the conical dendrons with diethylene glycol allowed the encapsulation of LiOTf and RbOTf in the center of the hollow sphere. These expts. showed that hollow spheres function as supramol. dendritic capsules and therefore are expected to display functions complementary to those of other related mol. and supramol. structures.
- 40Bates, M. W.; Lequieu, J.; Barbon, S. M.; Lewis, R. M.; Delaney, K. T.; Anastasaki, A.; Hawker, C. J.; Fredrickson, G. H.; Bates, C. M. Stability of the A15 Phase in Diblock Copolymer Melts. Proc. Natl. Acad. Sci. U.S.A. 2019, 116 (27), 13194– 13199, DOI: 10.1073/pnas.1900121116Google Scholar40https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXht1ykt7jI&md5=4a1ba54de2f345473cc0dd3fb57e218bStability of the A15 phase in diblock copolymer meltsBates, Morgan W.; Lequieu, Joshua; Barbon, Stephanie M.; Lewis, Ronald M., III; Delaney, Kris T.; Anastasaki, Athina; Hawker, Craig J.; Fredrickson, Glenn H.; Bates,, Christopher M.Proceedings of the National Academy of Sciences of the United States of America (2019), 116 (27), 13194-13199CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)The self-assembly of block polymers into well-ordered nanostructures underpins their utility across fundamental and applied polymer science, yet only a handful of equil. morphologies are known with the simplest AB-type materials. Here, we report the discovery of the A15 sphere phase in single-component diblock copolymer melts comprising poly(dodecyl acrylate)-block-poly(lactide). A systematic exploration of phase space revealed that A15 forms across a substantial range of minority lactide block vol. fractions (fL = 0.25 - 0.33) situated between the σ-sphere phase and hexagonally close-packed cylinders. SCF theory rationalizes the thermodn. stability of A15 as a consequence of extreme conformational asymmetry. The exptl. obsd. A15-disorder phase transition is not captured using mean-field approxns. but instead arises due to compn. fluctuations as evidenced by fully fluctuating field-theoretic simulations. This combination of expts. and field-theoretic simulations provides rational design rules that can be used to generate unique, polymer-based mesophases through self-assembly.
- 41Watanabe, M.; Asai, Y.; Suzuki, J.; Takano, A.; Matsushita, Y. Frank-Kasper A15 Phase Formed in ABn Block-Graft Copolymers with Large Numbers of Graft Chains. Macromolecules 2020, 53 (22), 10217– 10224, DOI: 10.1021/acs.macromol.0c01097Google Scholar41https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXit1SgtbnM&md5=61871cdf52f2faa1933af1119d88a53bFrank-Kasper A15 Phase Formed in ABn Block-Graft Copolymers with Large Numbers of Graft ChainsWatanabe, Momoka; Asai, Yusuke; Suzuki, Jiro; Takano, Atsushi; Matsushita, YushuMacromolecules (Washington, DC, United States) (2020), 53 (22), 10217-10224CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)Microphase-sepd. structures of a series of ABn block-graft copolymers were studied by transmission electron microscopy (TEM) coupled with small-angle X-ray scattering (SAXS). Five block-graft copolymers composed of the same polystyrene (S) backbone having polyisoprene (I) grafts with different chain lengths, wherein the nos. of grafts are almost const. (38 on av.), were synthesized by living anionic polymns., resulting in coverage of the polystyrene compn. range 0.32 ≤ φS ≤ 0.91. It was confirmed from the TEM observation that three low φS samples with φS of 0.32, 0.37, and 0.39 show complex spherical structures, while the sample with an φS of 0.57 reveals a hexagonal assembly of hexagonal rods of S in an I matrix, and the sample with φS of 0.91 exhibits inverse morphologies having rods of I in an S matrix. From detailed TEM and SAXS investigation combined with simulations, it has been found that the spherical structures formed from the samples with φS of 0.32 and 0.37 are both confirmed to have the structural feature of the Frank-Kasper A15 phase, which possesses the structural symmetry of the Pm3n space group.
- 42Montis, R.; Fusaro, L.; Falqui, A.; Hursthouse, M. B.; Tumanov, N.; Coles, S. J.; Threlfall, T. L.; Horton, P. N.; Sougrat, R.; Lafontaine, A.; Coquerel, G.; Rae, A. D. Complex Structures Arising from the Self-Assembly of a Simple Organic Salt. Nature 2021, 590 (7845), 275– 278, DOI: 10.1038/s41586-021-03194-yGoogle Scholar42https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXjslKnsrc%253D&md5=11b758eb57af740e61b8dc421f7460dfComplex structures arising from the self-assembly of a simple organic saltMontis, Riccardo; Fusaro, Luca; Falqui, Andrea; Hursthouse, Michael B.; Tumanov, Nikolay; Coles, Simon J.; Threlfall, Terry L.; Horton, Peter N.; Sougrat, Rachid; Lafontaine, Anais; Coquerel, Gerard; Rae, A. DavidNature (London, United Kingdom) (2021), 590 (7845), 275-278CODEN: NATUAS; ISSN:0028-0836. (Nature Research)Mol. self-assembly is the spontaneous assocn. of simple mols. into larger and ordered structures1. It is the basis of several natural processes, such as the formation of colloids, crystals, proteins, viruses and double-helical DNA2. Mol. self-assembly has inspired strategies for the rational design of materials with specific chem. and phys. properties3, and is one of the most important concepts in supramol. chem. Although mol. self-assembly has been extensively investigated, understanding the rules governing this phenomenon remains challenging. Here we report on a simple hydrochloride salt of fampridine that crystallizes as four different structures, two of which adopt unusual self-assemblies consisting of polyhedral clusters of chloride and pyridinium ions. These two structures represent Frank-Kasper (FK) phases of a small and rigid org. mol. Although discovered in metal alloys4,5 more than 60 years ago, FK phases have recently been obsd. in several classes of supramol. soft matter6-11 and in gold nanocrystal superlattices12 and remain the object of recent discoveries13. In these systems, atoms or spherical assemblies of mols. are packed to form polyhedra with coordination nos. 12, 14, 15 or 16. The two FK structures reported here crystallize from a dense liq. phase and show a complexity that is generally not obsd. in small rigid org. mols. Investigation of the precursor dense liq. phase by cryogenic electron microscopy reveals the presence of spherical aggregates with sizes ranging between 1.5 and 4.6 nm. These structures, together with the exptl. procedure used for their prepn., invite interesting speculation about their formation and open different perspectives for the design of org. cryst. materials.
- 43Kim, S. A.; Jeong, K.-J.; Yethiraj, A.; Mahanthappa, M. K. Low-Symmetry Sphere Packings of Simple Surfactant Micelles Induced by Ionic Sphericity. Proc. Natl. Acad. Sci. U.S.A. 2017, 114 (16), 4072– 4077, DOI: 10.1073/pnas.1701608114Google Scholar43https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXlsV2ntr8%253D&md5=793e22c1a4dcd276a815bb1ab3e4f973Low-symmetry sphere packings of simple surfactant micelles induced by ionic sphericityKim, Sung A.; Jeong, Kyeong-Jun; Yethiraj, Arun; Mahanthappa, Mahesh K.Proceedings of the National Academy of Sciences of the United States of America (2017), 114 (16), 4072-4077CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)Supramol. self-assembly enables access to designer soft materials that typically exhibit high-symmetry packing arrangements, which optimize the interactions between their mesoscopic constituents over multiple length scales. The authors report the discovery of an ionic small mol. surfactant that undergoes H2O-induced self-assembly into spherical micelles, which pack into a previously unknown, low-symmetry lyotropic liq. cryst. Frank-Kasper σ phase. Small-angle x-ray scattering studies reveal that this complex phase is characterized by a gigantic tetragonal unit cell, in which 30 sub-2-nm quasispherical micelles of 5 discrete sizes are arranged into a tetrahedral close packing, with exceptional translational order over length scales exceeding 100 nm. Varying the relative concns. of H2O and surfactant in these lyotropic phases also triggers formation of the related Frank-Kasper A15 sphere packing as well as a common bcc. structure. Mol. dynamics simulations reveal that the symmetry breaking that drives the formation of the σ and A15 phases arises from minimization of local deviations in surfactant headgroup and counterion solvation to maintain a nearly spherical counterion atm. around each micelle, while maximizing counterion-mediated electrostatic cohesion among the ensemble of charged particles.
- 44Huang, M.; Hsu, C.-H.; Wang, J.; Mei, S.; Dong, X.; Li, Y.; Li, M.; Liu, H.; Zhang, W.; Aida, T.; Zhang, W.-B.; Yue, K.; Cheng, S. Z. D. Selective Assemblies of Giant Tetrahedra via Precisely Controlled Positional Interactions. Science 2015, 348 (6233), 424– 428, DOI: 10.1126/science.aaa2421Google Scholar44https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXmslOntrY%253D&md5=10e120e314fe650268decdd8dd5a23b4Selective assemblies of giant tetrahedra via precisely controlled positional interactionsHuang, Mingjun; Hsu, Chih-Hao; Wang, Jing; Mei, Shan; Dong, Xuehui; Li, Yiwen; Li, Mingxuan; Liu, Hao; Zhang, Wei; Aida, Takuzo; Zhang, Wen-Bin; Yue, Kan; Cheng, Stephen Z. D.Science (Washington, DC, United States) (2015), 348 (6233), 424-428CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Self-assembly of rigid building blocks with explicit shape and symmetry is substantially influenced by the geometric factors and remains largely unexplored. The authors report the selective assembly behaviors of a class of precisely defined, nanosized giant tetrahedra constructed by placing different polyhedral oligomeric silsesquioxane (POSS) mol. nanoparticles at the vertexes of a rigid tetrahedral framework. Designed symmetry breaking of these giant tetrahedra introduces precise positional interactions and results in diverse selectively assembled, highly ordered supramol. lattices including a Frank-Kasper A15 phase, which resembles the essential structural features of certain metal alloys but at a larger length scale. These results demonstrate the power of persistent mol. geometry with balanced enthalpy and entropy in creating thermodynamically stable supramol. lattices with properties distinct from those of other self-assembling soft materials.
- 45Su, Z.; Hsu, C.-H.; Gong, Z.; Feng, X.; Huang, J.; Zhang, R.; Wang, Y.; Mao, J.; Wesdemiotis, C.; Li, T.; Seifert, S.; Zhang, W.; Aida, T.; Huang, M.; Cheng, S. Z. D. Identification of a Frank–Kasper Z Phase from Shape Amphiphile Self-Assembly. Nat. Chem. 2019, 11 (10), 899– 905, DOI: 10.1038/s41557-019-0330-xGoogle Scholar45https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhvVGgurfL&md5=942e450b5fd455f9b611e9a49aa651dfIdentification of a Frank-Kasper Z phase from shape amphiphile self-assemblySu, Zebin; Hsu, Chih-Hao; Gong, Zihao; Feng, Xueyan; Huang, Jiahao; Zhang, Ruimeng; Wang, Yu; Mao, Jialin; Wesdemiotis, Chrys; Li, Tao; Seifert, Soenke; Zhang, Wei; Aida, Takuzo; Huang, Mingjun; Cheng, Stephen Z. D.Nature Chemistry (2019), 11 (10), 899-905CODEN: NCAHBB; ISSN:1755-4330. (Nature Research)Frank-Kasper phases, a family of ordered structures formed from particles with spherical motifs, are found in a host of materials, such as metal alloys, inorg. colloids and various types of soft matter. All the exptl. obsd. Frank-Kasper phases can be constructed from the basic units of three fundamental structures called the A15, C15 and Z phases. The Z phase, typically obsd. in metal alloys, is assocd. with a relatively large vol. ratio between its constituents, and this constraint inhibits its formation in most self-assembled single-component soft-matter systems. We have assembled a series of nanosized shape amphiphiles that comprise a triphenylene core and six polyhedral oligomeric silsesquioxane cages grafted onto it through linkers to give a variety of unconventional structures, which include the Z phase. This structure was obtained through fine tuning of the linker lengths between the core and the peripheral polyhedral oligomeric silsesquioxane cages, and exhibits a relatively large vol. asymmetry between its constituent polyhedral particle motifs.
- 46Chen, C.; Poppe, M.; Poppe, S.; Wagner, M.; Tschierske, C.; Liu, F. Tetrahedral liquid-crystalline networks: an A15-like Frank-Kasper Phase based on rod-packing. Angew. Chem., Int. Ed. 2022, 61 (27), e202203447 DOI: 10.1002/anie.202203447Google ScholarThere is no corresponding record for this reference.
- 47Lin, H.; Lee, S.; Sun, L.; Spellings, M.; Engel, M.; Glotzer, S. C.; Mirkin, C. A. Clathrate Colloidal Crystals. Science 2017, 355 (6328), 931– 935, DOI: 10.1126/science.aal3919Google Scholar47https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXjsVCgsr8%253D&md5=801bf70967e15228884670bc0dc49f78Clathrate colloidal crystalsLin, Haixin; Lee, Sangmin; Sun, Lin; Spellings, Matthew; Engel, Michael; Glotzer, Sharon C.; Mirkin, Chad A.Science (Washington, DC, United States) (2017), 355 (6328), 931-935CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)DNA-programmable assembly was used to deliberately synthesize hundreds of different colloidal crystals spanning dozens of symmetries, but the complexity of the achieved structures has so far been limited to small unit cells. DNA-modified triangular bipyramids (∼250-nm long edge, 177-nm short edge) were assembled into clathrate architectures. Electron microscopy images revealed that ≥3 different structures form as large single-domain architectures or as multidomain materials. Ordered assemblies, isostructural to clathrates, were identified with the help of mol. simulations and geometric anal. These structures are the most sophisticated architectures made via programmable assembly, and their formation can be understood based on the shape of the nanoparticle building blocks and mode of DNA functionalization.
- 48Girard, M.; Wang, S.; Du, J. S.; Das, A.; Huang, Z.; Dravid, V. P.; Lee, B.; Mirkin, C. A.; De La Cruz, M. O. Particle Analogs of Electrons in Colloidal Crystals. Science 2019, 364 (6446), 1174– 1178, DOI: 10.1126/science.aaw8237Google Scholar48https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhtlKqsL7M&md5=e2767780ae789f4b14ef9f93710ffcd1Particle analogs of electrons in colloidal crystalsGirard, Martin; Wang, Shunzhi; Du, Jingshan S.; Das, Anindita; Huang, Ziyin; Dravid, Vinayak P.; Lee, Byeongdu; Mirkin, Chad A.; Olvera de la Cruz, MonicaScience (Washington, DC, United States) (2019), 364 (6446), 1174-1178CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)A versatile method for the design of colloidal crystals involves the use of DNA as a particle-directing ligand. With such systems, DNA-nanoparticle conjugates are considered programmable atom equiv. (PAEs), and design rules have been devised to engineer crystn. outcomes. This work shows that when reduced in size and DNA grafting d., PAEs behave as electron equiv. (EEs), roaming through and stabilizing the lattices defined by larger PAEs, as electrons do in metals in the classical picture. This discovery defines a new property of colloidal crystals-metallicity-that is characterized by the extent of EE delocalization and diffusion. As the no. of strands increases or the temp. decreases, the EEs localize, which is structurally reminiscent of a metal-insulator transition. Colloidal crystal metallicity, therefore, provides new routes to metallic, intermetallic, and compd. phases.
- 49Wang, S.; Lee, S.; Du, J. S.; Partridge, B. E.; Cheng, H. F.; Zhou, W.; Dravid, V. P.; Lee, B.; Glotzer, S. C.; Mirkin, C. A. The Emergence of Valency in Colloidal Crystals through Electron Equivalents. Nat. Mater. 2022, 21 (5), 580– 587, DOI: 10.1038/s41563-021-01170-5Google Scholar49https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38Xht1KqsL4%253D&md5=f453edd0c938eb145ae76fc34271fbd0The emergence of valency in colloidal crystals through electron equivalentsWang, Shunzhi; Lee, Sangmin; Du, Jingshan S.; Partridge, Benjamin E.; Cheng, Ho Fung; Zhou, Wenjie; Dravid, Vinayak P.; Lee, Byeongdu; Glotzer, Sharon C.; Mirkin, Chad A.Nature Materials (2022), 21 (5), 580-587CODEN: NMAACR; ISSN:1476-1122. (Nature Portfolio)Colloidal crystal engineering of complex, low-symmetry architectures is challenging when isotropic building blocks are assembled. Here we describe an approach to generating such structures based upon programmable atom equiv. (nanoparticles functionalized with many DNA strands) and mobile electron equiv. (small particles functionalized with a low no. of DNA strands complementary to the programmable atom equiv.). Under appropriate conditions, the spatial distribution of the electron equiv. breaks the symmetry of isotropic programmable atom equiv., akin to the anisotropic distribution of valence electrons or coordination sites around a metal atom, leading to a set of well-defined coordination geometries and access to three new low-symmetry cryst. phases. All three phases represent the first examples of colloidal crystals, with two of them having elemental analogs (body-centered tetragonal and high-pressure gallium), while the third (triple double-gyroid structure) has no known natural equiv. This approach enables the creation of complex, low-symmetry colloidal crystals that might find use in various technologies.
- 50Fang, Q.; Zhu, G.; Xue, M.; Sun, J.; Wei, Y.; Qiu, S.; Xu, R. A Metal–Organic Framework with the Zeolite MTN Topology Containing Large Cages of Volume 2.5 nm3. Angew. Chem., Int. Ed. 2005, 44 (25), 3845– 3848, DOI: 10.1002/anie.200462260Google ScholarThere is no corresponding record for this reference.
- 51Férey, G.; Serre, C.; Mellot-Draznieks, C.; Millange, F.; Surblé, S.; Dutour, J.; Margiolaki, I. A Hybrid Solid with Giant Pores Prepared by a Combination of Targeted Chemistry, Simulation, and Powder Diffraction. Angew. Chem., Int. Ed. 2004, 43 (46), 6296– 6301, DOI: 10.1002/anie.200460592Google Scholar51https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXhtFWrtL7J&md5=7200674db845103909fe0af6ea2f7e01Molecular modeling: A hybrid solid with giant pores prepared by a combination of targeted chemistry, simulation, and powder diffractionFerey, Gerard; Serre, Christian; Mellot-Draznieks, Caroline; Millange, Franck; Surble, Suzy; Dutour, Julien; Margiolaki, IreneAngewandte Chemie, International Edition (2004), 43 (46), 6296-6301CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)The assocn. of a chromium(III) trimeric building unit and 1,3,5-benzenetricarboxylate led to the powd. solid MIL-100. Simulations provided a crystal structure soln., which matched the exptl. powder XRD pattern. This unique simulation/diffraction combination allowed the structure detn. of a giant-pore solid with a zeotype architecture, built up from hybrid supertetrahedra.
- 52Férey, G.; Mellot-Draznieks, C.; Serre, C.; Millange, F.; Dutour, J.; Surblé, S.; Margiolaki, I. A Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area. Science 2005, 309 (5743), 2040– 2042, DOI: 10.1126/science.1116275Google Scholar52https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXhtVWntL3E&md5=6313e7e95b0edca92bb34df3f0c9752dA Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface AreaFerey, G.; Mellot-Draznieks, C.; Serre, C.; Millange, F.; Dutour, J.; Surble, S.; Margiolaki, I.Science (Washington, DC, United States) (2005), 309 (5743), 2040-2042CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)We combined targeted chem. and computational design to create a crystal structure for porous chromium terephthalate, MIL-101, with very large pore sizes and surface area. Its zeotype cubic structure has a giant cell vol. (∼702,000 cubic angstroms), a hierarchy of extra-large pore sizes (∼30 to 34 angstroms), and a Langmuir surface area for N2 of ∼5900 ± 300 square meters per g. Beside the usual properties of porous compds., this solid has potential as a nanomold for monodisperse nanomaterials, as illustrated here by the incorporation of Keggin polyanions within the cages.
- 53Park, Y. K.; Choi, S. B.; Kim, H.; Kim, K.; Won, B.; Choi, K.; Choi, J.; Ahn, W.; Won, N.; Kim, S.; Jung, D. H.; Choi, S.; Kim, G.; Cha, S.; Jhon, Y. H.; Yang, J. K.; Kim, J. Crystal Structure and Guest Uptake of a Mesoporous Metal–Organic Framework Containing Cages of 3.9 and 4.7 nm in Diameter. Angew. Chem., Int. Ed. 2007, 46 (43), 8230– 8233, DOI: 10.1002/anie.200702324Google Scholar53https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXhtlCkur7L&md5=e07d391f92e24f51a87523b24f935fcaCrystal structure and guest uptake of a mesoporous metal-organic framework containing cages of 3.9 and 4.7 nm in diameterPark, Young Kwan; Choi, Sang Beom; Kim, Hyunuk; Kim, Kimoon; Won, Byoung-Ho; Choi, Kihang; Choi, Jung-Sik; Ahn, Wha-Seung; Won, Nayoun; Kim, Sungjee; Jung, Dong, Hyun; Choi, Seung-Hoon; Kim, Ghyung-Hwa; Cha, Sun-Shin; Jhon, Young Ho; Yang, Jin KukAngewandte Chemie, International Edition (2007), 46 (43), 8230-8233CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)A new mesoporous metal-org. (MOF) framework that is mainly composed of Tb3+ ions and tripodal 1,3,5-triazine-2,4,6-tri-p-benzoate ligands has cages of 3.9 and 4.7 nm in diam. The evacuated framework is robust and can accommodate gases (N2, CO2) or ferrocene mols., as verified by gas-sorption measurements and luminescence studies.
- 54Kang, Y.; Wang, F.; Zhang, J.; Bu, X. Luminescent MTN -Type Cluster–Organic Framework with 2.6 nm Cages. J. Am. Chem. Soc. 2012, 134 (43), 17881– 17884, DOI: 10.1021/ja308801nGoogle Scholar54https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhsFSgs7fP&md5=7ebf5d1388492a8d4d9c86f3a26602ceLuminescent MTN-Type Cluster-Organic Framework with 2.6 nm CagesKang, Yao; Wang, Fei; Zhang, Jian; Bu, XianhuiJournal of the American Chemical Society (2012), 134 (43), 17881-17884CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)From a basic tetrahedral Cu4I4 cluster, a new MTN-type cluster-org. framework [Cu4I4(dabco)2]n (COZ-1) contg. giant 64512 and 512 cages was successfully constructed. The 64512 cage has an inner diam. of 2.6 nm and a large pore vol. of 9.2 nm3; these tetrahedral Cu4I4 clusters with bulky size offer new opportunities for not only the formation of 4-connected zeotype structures but also the integration of porosity and photoluminescent properties from both the cluster and the framework.
- 55Thorp-Greenwood, F. L.; Kulak, A. N.; Hardie, M. J. Three-Dimensional Silver-Dabco Coordination Polymers with Zeolitic or Three-Connected Topology. Cryst. Growth Des. 2014, 14 (11), 5361– 5365, DOI: 10.1021/cg501231vGoogle Scholar55https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhsl2hsLfO&md5=e8fd9d3d6bca43d21f308f471bd69de8Three-Dimensional Silver-dabco Coordination Polymers with Zeolitic or Three-Connected TopologyThorp-Greenwood, Flora L.; Kulak, Alexander N.; Hardie, Michaele J.Crystal Growth & Design (2014), 14 (11), 5361-5365CODEN: CGDEFU; ISSN:1528-7483. (American Chemical Society)The simple linear linking ligand diazabicyclo[2.2.2]octane (dabco) combines with silver(I) to form three-dimensional (3D) coordination polymers which have either a zeolitic mtn topol. structure or a (10,3)-b ths network according to the counteranion used. The tetrahedral anions BF4- or ReO4- promote formation of [Ag(dabco)2]·X, which has a 3D four-connected mtn framework of fused 512 and 64512 cages, and the material shows modest absorption of iodine. The bulky anion [Co(C2B9H11)2]- and an excess of dabco promote formation of complex [Ag2(dabco)3(CH3CN)2]·2[Co(C2B9H11)2] with a three-connected (10,3)-b network, while use of 1 equiv of dabco gives a previously reported [Ag(dabco)]·[Co(C2B9H11)2], which has a one-dimensional coordination chain structure.
- 56Park, K. S.; Ni, Z.; Côté, A. P.; Choi, J. Y.; Huang, R.; Uribe-Romo, F. J.; Chae, H. K.; O’Keeffe, M.; Yaghi, O. M. Exceptional Chemical and Thermal Stability of Zeolitic Imidazolate Frameworks. Proc. Natl. Acad. Sci. U.S.A. 2006, 103 (27), 10186– 10191, DOI: 10.1073/pnas.0602439103Google Scholar56https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XntlKjtbo%253D&md5=c28cd5862d4765fe4e4937195f5bb4dfExceptional chemical and thermal stability of zeolitic imidazolate frameworksPark, Kyo Sung; Ni, Zheng; Cote, Adrien P.; Choi, Jae Yong; Huang, Rudan; Uribe-Romo, Fernando J.; Chae, Hee K.; O'Keeffe, Michael; Yaghi, Omar M.Proceedings of the National Academy of Sciences of the United States of America (2006), 103 (27), 10186-10191CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)Twelve zeolitic imidazolate frameworks (ZIFs; termed ZIF-1 to -12) were synthesized as crystals by copolymn. of either Zn(II) (ZIF-1 to -4, -6 to -8, and -10 to -11) or Co(II) (ZIF-9 and -12) with imidazolate-type links. The ZIF crystal structures are based on the nets of seven distinct aluminosilicate zeolites: tetrahedral Si(Al) and the bridging O are replaced with transition metal ion and imidazolate link, resp. One example of mixed-coordination imidazolate of Zn(II) and In(III) (ZIF-5) based on the garnet net is reported. Study of the gas adsorption and thermal and chem. stability of two prototypical members, ZIF-8 and -11, demonstrated their permanent porosity (Langmuir surface area = 1,810 m2/g), high thermal stability (up to 550°), and remarkable chem. resistance to boiling alk. H2O and org. solvents.
- 57O’Keeffe, M.; Adams, G. B.; Sankey, O. F. Duals of Frank-Kasper Structures as C, Si and Ge Clathrates: Energetics and Structure. Philos. Mag. Lett. 1998, 78 (1), 21– 28, DOI: 10.1080/095008398178219Google ScholarThere is no corresponding record for this reference.
- 58Thomson, W. On the division of space with minimum partitional area. Acta Math. 1887, 11, 121– 134, DOI: 10.1007/BF02612322Google ScholarThere is no corresponding record for this reference.
- 59Gray, J. Parsimonious Polyhedra. Nature 1994, 367, 598– 599, DOI: 10.1038/367598a0Google ScholarThere is no corresponding record for this reference.
- 60Weaire, D.; Phelan, R. A Counter-Example to Kelvin’s Conjecture on Minimal Surfaces. Philos. Mag. Lett. 1994, 69 (2), 107– 110, DOI: 10.1080/09500839408241577Google Scholar60https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2cXktFyksL0%253D&md5=0168c197b0e37ea4abe7f673b900cb07A counter-example to Kelvin's conjecture on minimal surfacesWeaire, D.; Phelan, R.Philosophical Magazine Letters (1994), 69 (2), 107-10CODEN: PMLEEG; ISSN:0950-0839.Kelvin's conjecture, that a bcc. arrangement of his minimal tetrakaidecahedron divides space into equal cells of min. surface area, has stood for over one hundred years. The authors have found a counter-example, in the form of a structure analogous to that of some clathrate compds. and also related to the β-tungsten structure. Its surface area is approx. 0.3% less than that of Kelvin's structure.
- 61Gabbrielli, R.; Meagher, A. J.; Weaire, D.; Brakke, K. A.; Hutzler, S. An Experimental Realization of the Weaire–Phelan Structure in Monodisperse Liquid Foam. Philos. Mag. Lett. 2012, 92 (1), 1– 6, DOI: 10.1080/09500839.2011.645898Google Scholar61https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhtFWrtbk%253D&md5=ad54919fd4ace7e183cf17a8cdaf2e14An experimental realization of the Weaire-Phelan structure in monodisperse liquid foamGabbrielli, Ruggero; Meagher, Aaron J.; Weaire, Denis; Brakke, Kenneth A.; Hutzler, StefanPhilosophical Magazine Letters (2012), 92 (1), 1-6CODEN: PMLEEG; ISSN:0950-0839. (Taylor & Francis Ltd.)The Weaire-Phelan (WP) structure is the lowest energy structure known of an ideal monodisperse foam in the dry limit. To date, it has not been realized in the lab. Instead Lord Kelvin's 1887 structure, which it supplanted in 1994, has repeatedly been found in attempts to produce an ordered structure. This paradox is attributable to the flat walls of the containers used, with which the Kelvin structure is more compatible. Accordingly, we have fabricated a patterned mold whose faceted walls conform to the WP geometry, and thereby succeeded in inducing the formation of perfect crystals of the WP structure. Foam samples consisted of approx. 1500 bubbles. Vibrations favored crystn.
- 62Bacsa, J.; Less, R. J.; Skelton, H. E.; Soracevic, Z.; Steiner, A.; Wilson, T. C.; Wood, P. T.; Wright, D. S. Assembly of the First Fullerene-Type Metal–Organic Frameworks Using a Planar Five-Fold Coordination Node. Angew. Chem., Int. Ed. 2011, 50 (36), 8279– 8282, DOI: 10.1002/anie.201102783Google Scholar62https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXptlaksrc%253D&md5=d015749e01eaf82d767ed559282a6ec3Assembly of the First Fullerene-Type Metal-Organic Frameworks Using a Planar Five-Fold Coordination NodeBacsa, John; Less, Robert J.; Skelton, Helen E.; Soracevic, Zlatko; Steiner, Alexander; Wilson, Thomas C.; Wood, Paul T.; Wright, Dominic S.Angewandte Chemie, International Edition (2011), 50 (36), 8279-8282, S8279/1-S8279/4CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)A fullerene-type metal-org. framework was constructed using the planar pentacyanocyclopentadienide ligand. Recrystn. of sodium pentacyanocyclopentadienide in MeNO2 by vapor diffusion of Et2O resulted in the formation of the metal-org. framework complex [Na46(L)48][Na2]·xMeNO2·yEt2O which was structurally characterized.
- 63Zhang, W.; Wang, K.; Li, J.; Lin, Z.; Song, S.; Huang, S.; Liu, Y.; Nie, F.; Zhang, Q. Stabilization of the Pentazolate Anion in a Zeolitic Architecture with Na20 N60 and Na24 N60 Nanocages. Angew. Chem., Int. Ed. 2018, 57 (10), 2592– 2595, DOI: 10.1002/anie.201710602Google ScholarThere is no corresponding record for this reference.
- 64Schlenker, J. L.; Dwyer, F. G.; Jenkins, E. E.; Rohrbaugh, W. J.; Kokotailo, G. T.; Meier, W. M. Crystal Structure of a Synthetic High Silica Zeolite─ZSM-39. Nature 1981, 294 (5839), 340– 342, DOI: 10.1038/294340a0Google ScholarThere is no corresponding record for this reference.
- 65Baerlocher, C.; McCusker, L. Database of zeolite structures 2017 http://www.izastructure.org/databases/.Google ScholarThere is no corresponding record for this reference.
- 66Gómez-Gualdrón, D. A.; Cólon, Y. J.; Zhang, X.; Wang, T. C.; Chen, Y.-S.; Hupp, J. T.; Yildrim, T.; Farha, O. K.; Zhang, J.; Snurr, R. Q. Evaluating Topologically Diverse Metal–Organic Frameworks for Cryo-Adsorbed Hydrogen Storage. Energy Environ. Sci. 2016, 9 (10), 3279– 3289, DOI: 10.1039/C6EE02104BGoogle Scholar66https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhsVykt77O&md5=9793b81106ea8ffaaf36f07cc9f60b10Evaluating topologically diverse metal-organic frameworks for cryo-adsorbed hydrogen storageGomez-Gualdron, Diego A.; Colon, Yamil J.; Zhang, Xu; Wang, Timothy C.; Chen, Yu-Sheng; Hupp, Joseph T.; Yildirim, Taner; Farha, Omar K.; Zhang, Jian; Snurr, Randall Q.Energy & Environmental Science (2016), 9 (10), 3279-3289CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)Metal-org. frameworks (MOFs) are porous materials synthesized by combining inorg. and org. mol. building blocks into cryst. networks of distinct topologies. Due to the combinatorial possibilities, there are millions of possible MOF structures. Aiming to exploit their exceptional tunability, surface areas and pore vols., researchers have investigated MOFs for storage of gaseous fuels such as hydrogen for over a decade, but a suitable MOF to store hydrogen at ambient conditions has not yet been found. Here, we sought to rapidly det. the viability of using MOFs for hydrogen storage at recently proposed, cryogenic operating conditions. We constructed a large and structurally diverse set of 13 512 potential MOF structures based on 41 different topologies and used mol. simulation to det. MOF hydrogen deliverable capacities between 100 bar/77 K and 5 bar/160 K. The highest volumetric deliverable capacity was 57 g L-1 of MOF, which surpasses the 37 g L-1 of tank of the incumbent technol. (compressing hydrogen to 700 bar at ambient temp.). To validate our in silico MOF construction method, we synthesized a new isoreticular family of MOFs (she-MOF-x series) based on the she topol., which is extremely rare among MOFs. To validate our hydrogen storage predictions, we activated and measured hydrogen adsorption on she-MOF-1 and NU-1103. The latter MOF showed outstanding stability and a good combination of volumetric and gravimetric performance, presenting 43.2 g L-1 of MOF and 12.6 wt% volumetric and gravimetric deliverable capacities, resp.
- 67Moosavi, S. M.; Nandy, A.; Jablonka, K. M.; Ongari, D.; Janet, J. P.; Boyd, P. G.; Lee, Y.; Smit, B.; Kulik, H. J. Understanding the Diversity of the Metal-Organic Framework Ecosystem. Nat. Commun. 2020, 11 (1), 4068 DOI: 10.1038/s41467-020-17755-8Google Scholar67https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhs1WrsbfE&md5=d9ba7ae4ec44a4716746a8a21b2edf0dUnderstanding the diversity of the metal-organic framework ecosystemMoosavi, Seyed Mohamad; Nandy, Aditya; Jablonka, Kevin Maik; Ongari, Daniele; Janet, Jon Paul; Boyd, Peter G.; Lee, Yongjin; Smit, Berend; Kulik, Heather J.Nature Communications (2020), 11 (1), 4068CODEN: NCAOBW; ISSN:2041-1723. (Nature Research)Abstr.: Millions of distinct metal-org. frameworks (MOFs) can be made by combining metal nodes and org. linkers. At present, over 90,000 MOFs have been synthesized and over 500,000 predicted. This raises the question whether a new exptl. or predicted structure adds new information. For MOF chemists, the chem. design space is a combination of pore geometry, metal nodes, org. linkers, and functional groups, but at present we do not have a formalism to quantify optimal coverage of chem. design space. In this work, we develop a machine learning method to quantify similarities of MOFs to analyze their chem. diversity. This diversity anal. identifies biases in the databases, and we show that such bias can lead to incorrect conclusions. The developed formalism in this study provides a simple and practical guideline to see whether new structures will have the potential for new insights, or constitute a relatively small variation of existing structures.
- 68Wragg, D. S.; Morris, R. E.; Burton, A. W. Pure Silica Zeolite-Type Frameworks: A Structural Analysis. Chem. Mater. 2008, 20 (4), 1561– 1570, DOI: 10.1021/cm071824jGoogle Scholar68https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXntVemsg%253D%253D&md5=3c89ab0b413a8335cf5e5a4552348698Pure Silica Zeolite-type Frameworks: A Structural AnalysisWragg, David S.; Morris, Russell E.; Burton, Allen W.Chemistry of Materials (2008), 20 (4), 1561-1570CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Since the last major study of silicate crystal structures, many new pure SiO2 zeolite-type frameworks were discovered. These materials have many interesting properties that are dependent on their structure. The authors have brought together and analyzed the structures in 35 well-defined frameworks to see how they differ from one another depending on the synthetic route, template, calcination, and compn., and how they differ from the dense silicate phases previously examd. The grand mean values of the Si-O bond distance and the O-Si-O angle are 1.594 A and 109.5°, resp. The variation and flexibility of the Si-O-Si bond from 133.6 to 180° is discussed, as is the role of fluoride in influencing the O-Si-O bond angles in phases prepd. using HF and ammonium fluoride as mineralizers.
- 69Noh, K.; Lee, J.; Kim, J. Compositions and Structures of Zeolitic Imidazolate Frameworks. Isr. J. Chem. 2018, 58 (9–10), 1075– 1088, DOI: 10.1002/ijch.201800107Google Scholar69https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhvFKjtrvO&md5=4ed9488602f6da4d26bbbb60b8341804Compositions and Structures of Zeolitic Imidazolate FrameworksNoh, Kyungkyou; Lee, Jisu; Kim, JaheonIsrael Journal of Chemistry (2018), 58 (9-10), 1075-1088CODEN: ISJCAT; ISSN:0021-2148. (Wiley-VCH Verlag GmbH & Co. KGaA)A review. Zeolitic imidazolate frameworks (ZIFs), which are composed of point metal centers and imidazolate linkers, can adopt numerous three-dimensional structures. Their unique structures and porosity properties make ZIFs promising materials esp. for gas sepn. applications. Recently their unusual phase transition properties are getting research attention rapidly. Indeed, all the properties of ZIFs are dependent on their structures. Although some empirical rules are known for discovering new ZIFs, still scientific intuition and trials are necessary to find proper reaction conditions. Also, practical information should be extd. from the accumulate achievements and in turn, applied to further exploration. In this regard, this article analyses the structures, compns., and porosity of known ZIFs, where the relationship between imidazolates and topologies is described in detail.
- 70Lee, S.; Nam, D.; Yang, D. C.; Choe, W. Unveiling Hidden Zeolitic Imidazolate Frameworks Guided by Intuition-Based Geometrical Factors. Small 2023, 19 (15), 2300036 DOI: 10.1002/smll.202300036Google ScholarThere is no corresponding record for this reference.
- 71O’Keeffe, M. Tetrahedral Frameworks TX2 with T–X–T Angle = 180°. Mater. Res. Bull. 2006, 41 (5), 911– 915, DOI: 10.1016/j.materresbull.2005.12.013Google ScholarThere is no corresponding record for this reference.
- 72Hohenberg, P.; Kohn, W. Inhomogeneous Electron Gas. Phys. Rev. 1964, 136 (3B), B864– B871, DOI: 10.1103/PhysRev.136.B864Google ScholarThere is no corresponding record for this reference.
- 73Kamakoti, P.; Barckholtz, T. A. Role of Germanium in the Formation of Double Four Rings in Zeolites. J. Phys. Chem. C 2007, 111 (9), 3575– 3583, DOI: 10.1021/jp065092eGoogle Scholar73https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXitF2itLo%253D&md5=4cf1823da5d57f0168195c15e4f7a0b7Role of Germanium in the Formation of Double Four Rings in ZeolitesKamakoti, Preeti; Barckholtz, Timothy A.Journal of Physical Chemistry C (2007), 111 (9), 3575-3583CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)In recent years, novel zeolites contg. double four rings (D4Rs) were synthesized by introducing Ge into the synthesis mixt. While the structure-directing effects of Ge toward D4R contg. structures are known, little is known about the underlying chem. Plane wave d. functional theory calcns. were used to characterize and rationalize the site preferences, energies, and structural changes occurring when Ge is gradually substituted into the BEC framework up to 25% loadings. The calcns. show that the site preference and energies are strongly dictated by the intrinsic flexibility of a given T-O-T linkage (T = Si or Ge), coupled with its ability to relax to geometries preferred by Ge. Calcns. on small mol. fragments were used to explore the geometric variations in Ge-substituted zeolites and provide further insight into the role of Ge in stabilizing D4R units.
- 74Sastre, G.; Corma, A. Predicting Structural Feasibility of Silica and Germania Zeolites. J. Phys. Chem. C 2010, 114 (3), 1667– 1673, DOI: 10.1021/jp909348sGoogle Scholar74https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXhtFKjsA%253D%253D&md5=c366d86248e7ab7e09af0be1494e806fPredicting Structural Feasibility of Silica and Germania ZeolitesSastre, German; Corma, AvelinoJournal of Physical Chemistry C (2010), 114 (3), 1667-1673CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)High throughput exptl. techniques for zeolite synthesis, combined with the introduction of germanium in the synthesis gel, have allowed an increase in the no. of new zeolites, esp. of those contg. large and extralarge pores. Zeolite phases contg. Si/Ge as tetrahedral atoms stabilize certain unique topologies. One particular feature of Ge-contg. zeolites is the stabilization of small TOT (T = Si, Ge) angles compared to their silica counterparts. This study employs computational chem. techniques to calc. and rationalize the relative stability of zeolite phases as silicates and germanates. Atomistic force fields are used to simulate the structural properties of exptl. synthesized Si/Ge-contg. zeolites, and an ab initio Hartree-Fock methodol. is used to est. the energetics of TOT angles. It is shown that each particular topol. is only compatible with certain ranges of TOT angles, and, depending on the chem. compn., this induces stability or strain. A calcn. of the energetic penalty assocd. with TOT angles for the different chem. compns. at each topol. allows an est. of their feasibility. The results are in agreement with expts. and allow one to make predictions about feasibility of new SiO2 or GeO2 zeolite structures.
- 75Sartbaeva, A.; Wells, S. A.; Treacy, M. M. J.; Thorpe, M. F. The Flexibility Window in Zeolites. Nat. Mater. 2006, 5 (12), 962– 965, DOI: 10.1038/nmat1784Google Scholar75https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28Xht1Gku7bF&md5=ab90f15fc9eecd544d6249222427d6a5The flexibility window in zeolitesSartbaeva, Asel; Wells, Stephen A.; Treacy, M. M. J.; Thorpe, M. F.Nature Materials (2006), 5 (12), 962-965CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)A mol. geometric simulation of zeolite structures was carried out to rationalize hypothetical geometric structures of zeolite cages, based on energy minimization, in order to provide criteria capable of predicting new zeolite structures. All realizable zeolite framework structures showed a flexibility window over a range of densities. This flexibility window is conjectured to be a necessary structural feature that enables zeolite synthesis, and therefore provides a valuable selection criterion when evaluating hypothetical zeolite framework structures as potential synthetic targets. This flexibility is a general feature that exptl. densities of silica zeolites lie at the low-d. edge of this window because the pores are driven to their max. vol. by Coulomb inflation (i.e., repulsion, probably between oxygen anions). This is in contrast to most solids, which have the highest d. consistent with the local chem. and geometrical constraints.
- 76Liu, X.-Y.; Yan, X.-Y.; Liu, Y.; Qu, H.; Wang, Y.; Wang, J.; Guo, Q.-Y.; Lei, H.; Li, X.-H.; Bian, F.; Cao, X.-Y.; Zhang, R.; Wang, Y.; Huang, M.; Lin, Z.; Meijer, E. W.; Aida, T.; Kong, X.; Cheng, S. Z. D. Self-Assembled Soft Alloy with Frank–Kasper Phases beyond Metals. Nat. Mater. 2024, 23 (4), 570– 576, DOI: 10.1038/s41563-023-01796-7Google ScholarThere is no corresponding record for this reference.
- 77Sikirić, M. D.; Deza, M. Space Fullerenes: Computer Search for New Frank–Kasper Structures II. Struct. Chem. 2012, 23 (4), 1103– 1114, DOI: 10.1007/s11224-012-0005-3Google ScholarThere is no corresponding record for this reference.
- 78Kim, K.; Schulze, M. W.; Arora, A.; Lewis, R. M.; Hillmyer, M. A.; Dorfman, K. D.; Bates, F. S. Thermal Processing of Diblock Copolymer Melts Mimics Metallurgy. Science 2017, 356 (6337), 520– 523, DOI: 10.1126/science.aam7212Google Scholar78https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXmvVGnsL4%253D&md5=e4c0910b1cfe7651f2c414155d12e280Thermal processing of diblock copolymer melts mimics metallurgyKim, Kyungtae; Schulze, Morgan W.; Arora, Akash; Lewis, Ronald M., III; Hillmyer, Marc A.; Dorfman, Kevin D.; Bates, Frank S.Science (Washington, DC, United States) (2017), 356 (6337), 520-523CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Small-angle x-ray scattering expts. conducted with compositionally asym. low molar mass poly(isoprene)-b-poly(lactide) diblock copolymers reveal an extraordinary thermal history dependence. The development of distinct periodic cryst. or aperiodic quasicryst. states depends on how specimens are cooled from the disordered state to temps. below the order-disorder transition temp. Whereas direct cooling leads to the formation of documented morphologies, rapidly quenched samples that are then heated from low temp. form the hexagonal C14 and cubic C15 Laves phases commonly found in metal alloys. Self-consistent mean-field theory calcns. show that these, and other assocd. Frank-Kasper phases, have nearly degenerate free energies, suggesting that processing history drives the material into long-lived metastable states defined by self-assembled particles with discrete populations of vols. and polyhedral shapes.
- 79Materials Studio v7.0; Accelrys Software Inc.: San Diego, CA 92121, USA.Google ScholarThere is no corresponding record for this reference.
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- 1Zhou, H.-C.; Long, J. R.; Yaghi, O. M. Introduction to Metal–Organic Frameworks. Chem. Rev. 2012, 112 (2), 673– 674, DOI: 10.1021/cr300014x1https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38Xht1OjtLw%253D&md5=abf05fcd4ae6b394b7f1048a93f5ebbcIntroduction to Metal-Organic FrameworksZhou, Hong-Cai; Long, Jeffrey R.; Yaghi, Omar M.Chemical Reviews (Washington, DC, United States) (2012), 112 (2), 673-674CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review is presented on prepn., structure and application of Metal-Org. Frameworks.
- 2Moghadam, P. Z.; Li, A.; Wiggin, S. B.; Tao, A.; Maloney, A. G. P.; Wood, P. A.; Ward, S. C.; Fairen-Jimenez, D. Development of a Cambridge Structural Database Subset: A Collection of Metal–Organic Frameworks for Past, Present, and Future. Chem. Mater. 2017, 29 (7), 2618– 2625, DOI: 10.1021/acs.chemmater.7b004412https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXkt12rurc%253D&md5=377ebf2d805518194eb8cd0f9d3f3608Development of a Cambridge Structural Database Subset: A Collection of Metal-Organic Frameworks for Past, Present, and FutureMoghadam, Peyman Z.; Li, Aurelia; Wiggin, Seth B.; Tao, Andi; Maloney, Andrew G. P.; Wood, Peter A.; Ward, Suzanna C.; Fairen-Jimenez, DavidChemistry of Materials (2017), 29 (7), 2618-2625CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)The generation and characterization of the most complete collection of metal-org. frameworks (MOFs) maintained and updated by the Cambridge Crystallog. Data Center (CCDC) is reported. To set up this subset, the question was asked what is a MOF and a no. of look-for-MOF criteria embedded within a bespoke Cambridge Structural Database (CSD) Python API workflow was implemented to identify and ext. information on 69,666 MOF materials. The CSD MOF subset is updated regularly with subsequent MOF addns. to the CSD, bringing a unique record for all researchers working in the area of porous materials around the world, whether to perform high-throughput computational screening for materials discovery or to have a global view over the existing structures in a single resource. Using this resource, the authors then developed and used an array of computational tools to remove residual solvent mols. from the framework pores of all the MOFs identified and went on to analyze geometrical and phys. properties of nondisordered structures.
- 3Freund, R.; Canossa, S.; Cohen, S. M.; Yan, W.; Deng, H.; Guillerm, V.; Eddaoudi, M.; Madden, D. G.; Fairen-Jimenez, D.; Lyu, H.; Macreadie, L. K.; Ji, Z.; Zhang, Y.; Wang, B.; Haase, F.; Wöll, C.; Zaremba, O.; Andreo, J.; Wuttke, S.; Diercks, C. S. 25 Years of Reticular Chemistry. Angew. Chem., Int. Ed. 2021, 60 (45), 23946– 23974, DOI: 10.1002/anie.2021016443https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhs1emsrnM&md5=94a9c60f9ede4261e2e9a3a225d0004bThe 25 Years of Reticular ChemistryFreund, Ralph; Canossa, Stefano; Cohen, Seth M.; Yan, Wei; Deng, Hexiang; Guillerm, Vincent; Eddaoudi, Mohamed; Madden, David G.; Fairen-Jimenez, David; Lyu, Hao; Macreadie, Lauren K.; Ji, Zhe; Zhang, Yuanyuan; Wang, Bo; Haase, Frederik; Woll, Christof; Zaremba, Orysia; Andreo, Jacopo; Wuttke, Stefan; Diercks, Christian S.Angewandte Chemie, International Edition (2021), 60 (45), 23946-23974CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)A review. At its core, reticular chem. has translated the precision and expertise of org. and inorg. synthesis to the solid state. While initial excitement over metal-org. frameworks (MOFs) and covalent org. frameworks (COFs) was undoubtedly fueled by their unprecedented porosity and surface areas, the most profound scientific innovation of the field has been the elaboration of design strategies for the synthesis of extended cryst. solids through strong directional bonds. In this contribution we highlight the different classes of reticular materials that have been developed, how these frameworks can be functionalized, and how complexity can be introduced into their backbones. Finally, we show how the structural control over these materials is being extended from the mol. scale to their crystal morphol. and shape on the nanoscale, all the way to their shaping on the bulk scale.
- 4Kalmutzki, M. J.; Hanikel, N.; Yaghi, O. M. Secondary Building Units as the Turning Point in the Development of the Reticular Chemistry of MOFs. Sci. Adv. 2018, 4 (10), eaat9180 DOI: 10.1126/sciadv.aat9180There is no corresponding record for this reference.
- 5Lu, W.; Wei, Z.; Gu, Z.-Y.; Liu, T.-F.; Park, J.; Park, J.; Tian, J.; Zhang, M.; Zhang, Q.; Gentle Iii, T.; Bosch, M.; Zhou, H.-C. Tuning the Structure and Function of Metal–Organic Frameworks via Linker Design. Chem. Soc. Rev. 2014, 43 (16), 5561– 5593, DOI: 10.1039/C4CS00003J5https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXht1Slu7jK&md5=322785c0256204742e3e95e5d2d49914Tuning the structure and function of metal-organic frameworks via linker designLu, Weigang; Wei, Zhangwen; Gu, Zhi-Yuan; Liu, Tian-Fu; Park, Jinhee; Park, Jihye; Tian, Jian; Zhang, Muwei; Zhang, Qiang; Gentle III, Thomas; Bosch, Mathieu; Zhou, Hong-CaiChemical Society Reviews (2014), 43 (16), 5561-5593CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)A review. Metal-org. frameworks (MOFs) are constructed from metal ions/clusters coordinated by org. linkers (or bridging-ligands). The hallmark of MOFs is their permanent porosity, which is frequently found in MOFs constructed from metal-clusters. These clusters are often formed in situ, whereas the linkers are generally pre-formed. The geometry and connectivity of a linker dictate the structure of the resulting MOF. Adjustments of linker geometry, length, ratio, and functional-group can tune the size, shape, and internal surface property of a MOF for a targeted application. In this crit. review, the authors highlight advances in MOF synthesis focusing on linker design. Examples of building MOFs to reach unique properties, such as unprecedented surface area, pore aperture, mol. recognition, stability, and catalysis, through linker design are described. Further search for application-oriented MOFs through judicious selection of metal clusters and org. linkers is desirable. In this review, linkers are categorized as ditopic (Section 1), tritopic (Section 2), tetratopic (Section 3), hexatopic (Section 4), octatopic (Section 5), mixed (Section 6), desymmetrized (Section 7), metallo (Section 8), and N-heterocyclic linkers (Section 9).
- 6O’Keeffe, M.; Peskov, M. A.; Ramsden, S. J.; Yaghi, O. M. The Reticular Chemistry Structure Resource (RCSR) Database of, and Symbols for, Crystal Nets. Acc. Chem. Res. 2008, 41 (12), 1782– 1789, DOI: 10.1021/ar800124u6https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXht1SgsrjF&md5=392c624f403dd8457460a7649aa496f3The Reticular Chemistry Structure Resource (RCSR) database of, and symbols for, crystal netsO'Keeffe, Michael; Peskov, Maxim A.; Ramsden, Stuart J.; Yaghi, Omar M.Accounts of Chemical Research (2008), 41 (12), 1782-1789CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)During the past decade, interest has grown tremendously in the design and synthesis of cryst. materials constructed from mol. clusters linked by extended groups of atoms. Most notable are metal-org. frameworks (MOFs), in which polyat. inorg. metal-contg. clusters are joined by polytopic linkers. (Although these materials are sometimes referred to as coordination polymers, we prefer to differentiate them, because MOFs are based on strong linkages that yield robust frameworks.) The realization that MOFs could be designed and synthesized in a rational way from mol. building blocks led to the emergence of a discipline that we call reticular chem.MOFs can be represented as a special kind of graph called a periodic net. Such descriptions date back to the earliest crystallog. studies but have become much more common recently because thousands of new structures and hundreds of underlying nets have been reported. In the simplest cases (e.g., the structure of diamond), the atoms in the crystal become the vertices of the net, and bonds are the links (edges) that connect them. In the case of MOFs, polyat. groups act as the vertices and edges of the net.Because of the explosive growth in this area, a need has arisen for a universal system of nomenclature, classification, identification, and retrieval of these topol. structures. We have developed a system of symbols for the identification of three periodic nets of interest, and this system is now in wide use. In this Account, we explain the underlying methodol. of assigning symbols and describe the Reticular Chem. Structure Resource (RCSR), in which about 1600 such nets are collected and illustrated in a database that can be searched by symbol, name, keywords, and attributes. The resource also contains searchable data for polyhedra and layers.The database entries come from systematic enumerations or from known chem. compds. or both. In the latter case, refs. to occurrences are provided. We describe some crystallog., topol., and other attributes of nets and explain how they are reported in the database. We also describe how the database can be used as a tool for the design and structural anal. of new materials. Assocd. with each net is a natural tiling, which is a natural partition of space into space-filling tiles. The database allows export of data that can be used to analyze and illustrate such tilings.
- 7O’Keeffe, M. Design of MOFs and Intellectual Content in Reticular Chemistry: A Personal View. Chem. Soc. Rev. 2009, 38 (5), 1215– 1217, DOI: 10.1039/b802802h7https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXkvVamu78%253D&md5=3811ee3f78991faa0cd9e0524b6aee3cDesign of MOFs and intellectual content in reticular chemistry: a personal viewO'Keeffe, MichaelChemical Society Reviews (2009), 38 (5), 1215-1217CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)A review. This article gives a personal perspective on the ideas leading to the development of reticular chem. The feasibility of achieving targeted materials with predetd. metrics and functionality by designed synthesis is defended.
- 8Tranchemontagne, D. J.; Mendoza-Cortés, J. L.; O’Keeffe, M.; Yaghi, O. M. Secondary Building Units, Nets and Bonding in the Chemistry of Metal–Organic Frameworks. Chem. Soc. Rev. 2009, 38 (5), 1257– 1283, DOI: 10.1039/b817735j8https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXkvValsr8%253D&md5=3e03c5e2c057b36eb590c1904aa5e5a1Secondary building units, nets and bonding in the chemistry of metal-organic frameworksTranchemontagne, David J.; Mendoza-Cortes, Jose L.; O'Keeffe, Michael; Yaghi, Omar M.Chemical Society Reviews (2009), 38 (5), 1257-1283CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)This crit. review presents a comprehensive study of transition-metal carboxylate clusters which may serve as secondary building units (SBUs) towards construction and synthesis of metal-org. frameworks (MOFs). We describe the geometries of 131 SBUs, their connectivity and compn. This contribution presents a comprehensive list of the wide variety of transition-metal carboxylate clusters which may serve as secondary building units (SBUs) in the construction and synthesis of metal-org. frameworks. The SBUs discussed here were obtained from a search of mols. and extended structures archived in the Cambridge Structure Database (CSD, version 5.28, Jan. 2007) which included only crystals contg. metal carboxylate linkages (241 refs.).
- 9Jiang, H.; Alezi, D.; Eddaoudi, M. E. A reticular chemistry guide for the design of periodic solids. Nat. Rev. Mater. 2021, 6 (6), 466– 487, DOI: 10.1038/s41578-021-00287-y9https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhsFegurvL&md5=6e9a10dfa101cc33649d49856f859d01Review on reticular chemistry guide for the design of periodic solidsJiang, Hao; Alezi, Dalal; Eddaoudi, MohamedNature Reviews Materials (2021), 6 (6), 466-487CODEN: NRMADL; ISSN:2058-8437. (Nature Portfolio)A review. Abstr.: Reticular chem. - the linking of well-defined mol. building blocks by strong bonds into cryst. extended frameworks - has enabled the synthesis of diverse metal-org. frameworks (MOFs) and covalent org. frameworks, in which the pore shape, size and functionality can be tailored towards specific applications. Structural design methodologies are based on three main requisites: building blocks, targeted nets and isoreticular chem. In this Review, we highlight the well-developed and cutting-edge methodologies in reticular chem. for the structural design and discovery of periodic solids. We illustrate the diversity of building blocks and delineate the suitable blueprint nets - namely, edge-transitive nets - for the design of MOFs. These edge-transitive nets are classified into three categories to help rationalize existing MOFs and to provide guidelines for the design of new structures. Two emerging topol. concepts, namely, the merged-net approach and net-coded building units, are highlighted for their potential in synthesizing intricate or multi-component MOFs. We also consider isoreticular design strategies for the modification, expansion and contraction of building blocks, and identify challenges and opportunities in the assembly of increasingly intricate frameworks.
- 10Guillerm, V.; Kim, D.; Eubank, J. F.; Luebke, R.; Liu, X.; Adil, K.; Lah, M. S.; Eddaoudi, M. A Supermolecular Building Approach for the Design and Construction of Metal–Organic Frameworks. Chem. Soc. Rev. 2014, 43 (16), 6141– 6172, DOI: 10.1039/C4CS00135D10https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhtFehsbvO&md5=97bf12cb969bfc7f409f5f06facd593bA supermolecular building approach for the design and construction of metal-organic frameworksGuillerm, Vincent; Kim, Dongwook; Eubank, Jarrod F.; Luebke, Ryan; Liu, Xinfang; Adil, Karim; Lah, Myoung Soo; Eddaoudi, MohamedChemical Society Reviews (2014), 43 (16), 6141-6172CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)A review. In this review, the authors describe two recently implemented conceptual approaches facilitating the design and deliberate construction of metal-org. frameworks (MOFs), supermol. building block (SBB) and supermol. building layer (SBL) approaches. The authors' main objective is to offer an appropriate means to assist/aid chemists and material designers alike to rationally construct desired functional MOF materials, made-to-order MOFs. The authors introduce the concept of net-coded building units (net-cBUs), where precise embedded geometrical information codes uniquely and matchlessly a selected net, as a compelling route for the rational design of MOFs. This concept is based on employing pre-selected 0-periodic metal-org. polyhedra or 2-periodic metal-org. layers, SBBs or SBLs, resp., as a pathway to access the requisite net-cBUs. In this review, inspired by the authors' success with the original rht-MOF, the authors extrapolated the authors' strategy to other known MOFs via their deconstruction into more elaborate building units (polyhedra or layers) to (i) elucidate the unique relation between edge-transitive polyhedra or layers and minimal edge-transitive 3-periodic nets, and (ii) illustrate the potential of the SBB and SBL approaches as a rational pathway for the design and construction of 3-periodic MOFs. Using this design strategy, the authors have also identified several new hypothetical MOFs which are synthetically targetable.
- 11Kim, D.; Liu, X.; Lah, M. S. Topology Analysis of Metal–Organic Frameworks Based on Metal–Organic Polyhedra as Secondary or Tertiary Building Units. Inorg. Chem. Front. 2015, 2 (4), 336– 360, DOI: 10.1039/C4QI00236AThere is no corresponding record for this reference.
- 12Khobotov-Bakishev, A.; Hernández-López, L.; von Baeckmann, C.; Albalad, J.; Carné-Sánchez, A.; Maspoch, D. Metal–Organic Polyhedra as Building Blocks for Porous Extended Networks. Adv. Sci. 2022, 9 (11), 2104753 DOI: 10.1002/advs.202104753There is no corresponding record for this reference.
- 13Guillerm, V.; Eddaoudi, M. The Importance of Highly Connected Building Units in Reticular Chemistry: Thoughtful Design of Metal–Organic Frameworks. Acc. Chem. Res. 2021, 54 (17), 3298– 3312, DOI: 10.1021/acs.accounts.1c0021413https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhsVKrtL3K&md5=54b28aee95182a070397635423279566The Importance of Highly Connected Building Units in Reticular Chemistry: Thoughtful Design of Metal-Organic FrameworksGuillerm, Vincent; Eddaoudi, MohamedAccounts of Chemical Research (2021), 54 (17), 3298-3312CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)A review. The prediction of crystal structures assembled in three dimensions has been considered for a long time, simultaneously as a "chem. wasteland" and "a certain growth point of the chem. of the future". Less than 30 years after Roald Hoffmann's statement, we can categorically affirm that the raise of reticular chem. and introduction of metal-org. frameworks (MOFs) significantly tackled this tridimensional assembly issue. MOFs result from the assembly of org. polytopic org. ligands bridging metal nodes, clusters, chains or layers together into, mostly, 3-periodic open frameworks. They can exhibit extremely high porosity, offer great potential as revolutionary catalysts, drug carrier systems, sensors, smart materials, and of course, sepn. agents. Overall, the progressive development of reticular chem. has been a game changer in materials chem. during the last 25 years. Such diverse properties often result not only from the selected org. and inorg. mol. building blocks (MBBs), but also on their distribution within the framework. Indeed, the size, shape of porous system, influence the overall properties, as well as the location of the active sites. Therefore, in the continuity of achieving the crystn. of 3-periodic structures, chemists and crystal engineers faced the next challenge, summarized by John Maddox, "it remains in general impossible to predict the structure of even the simplest crystallog. solids from knowledge of their chem. compn.". This is where rational design takes place. In this account, we detail three specific approaches developed by our group to facilitate the design and assembly of finely tuned MOFs. All are based on careful geometrical consideration and a deep study and understanding of the existing nets, topologies. We recognized highly connected nets, if possible edge-transitive, are ideal blueprints, as their no. is limited in contrast to nets with lower connectivity. Therefore, we embarked in taking advantage of existing highly connected MBBs, or in parallel, promoting their formation to meet our requirements. This is achieved by utilizing externally decorated metal-org. polyhedra as supermol. building blocks (SBBs), serving as a net-coding building unit, comprising the requisite connectivity and directional information coding for the chosen nets. The SBB approach allowed the synthesis of several families of SBB based MOFs, including fcu, rht, and gea-MOFs, that are detailed here. The second strategy is directly inherited from the success of the SBB approach. Seeking for highly connected building units, our group naturally expanded its research focus to nets that can be deconstructed into layers, pillared in various ways. In the supermol. building layer (SBL) approach, the layers have an almost infinite connectivity, and the framework backbone is fixed in two dimensions while the third is free for pillar expansion and functionalization. The cases of trigonal pillaring leading to rtl, eea and apo MOFs, as well as the quadrangular pillaring leading to a family of tbo-MOFs is discussed here, along with recent cases of highly connected pillars in pek and aea-MOFs. Finally, our experience with highly coordinated MBBs led us to develop a novel way to use them as secondary building units of lower connectivity and unlock the possibility of assembling a novel class of zeolite-like MOFs (ZMOFs). The case of the Zr-sod-ZMOFs designed through a cantellation strategy is described as a future leading direction of MOFs design.
- 14Li, P.; Vermeulen, N. A.; Malliakas, C. D.; Gómez-Gualdrón, D. A.; Howarth, A. J.; Mehdi, B. L.; Dohnalkova, A.; Browning, N. D.; O’Keeffe, M.; Farha, O. K. Bottom-up construction of a superstructure in a porous uranium-organic crystal. Science 2017, 356 (6338), 624– 627, DOI: 10.1126/science.aam785114https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXnt1Chs78%253D&md5=ce8c4f6f63a111d50bcad772348d7c71Bottom-up construction of a superstructure in a porous uranium-organic crystalLi, Peng; Vermeulen, Nicolaas A.; Malliakas, Christos D.; Gomez-Gualdron, Diego A.; Howarth, Ashlee J.; Mehdi, B. Layla; Dohnalkova, Alice; Browning, Nigel D.; O'Keeffe, Michael; Farha, Omar K.Science (Washington, DC, United States) (2017), 356 (6338), 624-627CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Bottom-up construction of highly intricate structures from simple building blocks remains one of the most difficult challenges in chem. The authors report a structurally complex, mesoporous uranium-based metal-org. framework (MOF) made from simple starting components. The structure comprises 10 uranium nodes and seven tricarboxylate ligands (both crystallog. nonequivalent), resulting in a 173.3-Å cubic unit cell enclosing 816 uranium nodes and 816 org. linkers-the largest unit cell found to date for any nonbiol. material. The cuboctahedra organize into pentagonal and hexagonal prismatic secondary structures, which then form tetrahedral and diamond quaternary topologies with unprecedented complexity. This packing gave colossal icosidodecahedral and rectified hexakaidecahedral cavities with internal diams. of 5.0 nm and 6.2 nm, resp.-ultimately giving rise to the lowest-d. MOF reported to date.
- 15Barsukova, M.; Sapianik, A.; Guillerm, V.; Shkurenko, A.; Shaikh, A. C.; Parvatkar, P.; Bhatt, P. M.; Bonneau, M.; Alhaji, A.; Shekhah, O.; Balestra, S. R. G.; Semino, R.; Maurin, G.; Eddaoudi, M. Face-directed assembly of tailored isoreticular MOFs using centring structure-directing agents. Nat. Synth. 2024, 3 (1), 33– 46, DOI: 10.1038/s44160-023-00401-8There is no corresponding record for this reference.
- 16O’Keeffe, M. Crystal Structures as Periodic Foams and Vice Versa. In Foams and Emulsions; Sadoc, J. F.; Rivier, N., Eds.; Springer Netherlands: Dordrecht, 1999; pp; pp 403– 422.There is no corresponding record for this reference.
- 17Frank, F. C.; Kasper, J. S. Complex Alloy Structures Regarded as Sphere Packings. I. Definitions and Basic Principles. Acta Crystallogr. 1958, 11 (3), 184– 190, DOI: 10.1107/S0365110X5800048717https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaG1cXkvVCjsA%253D%253D&md5=7610405316848e64c343a39d887ba2d6Complex alloy structures regarded as sphere packings. I. Definitions and basic principlesFrank, F. C.; Kasper, J. S.Acta Crystallographica (1958), 11 (), 184-90CODEN: ACCRA9; ISSN:0365-110X.Complex alloy structures, particularly those of transition metals, are considered as detd. by the geometrical requirements for sphere packing. A characteristic of the class of structures discussed is that tetrahedral groupings of atoms occur everywhere in the structure, that is co.ovrddot.ordination polyhedra have only triangular faces. The topological and geometrical properties of such polyhedra are examd., and rules and theorems regarding them are deduced. Justification is given for the prominence of 4 such polyhedra (for co.ovrddot.ordination nos. of 12, 14, 15, and 16) in actual structures. General principles regarding the combination of these polyhedra into full structures are deduced, and necessary definitions are given for terms that facilitate the detailed discussion of this class of structures.
- 18Frank, F. C.; Kasper, J. S. Complex Alloy Structures Regarded as Sphere Packings. II. Analysis and Classification of Representative Structures. Acta Crystallogr. 1959, 12 (7), 483– 499, DOI: 10.1107/S0365110X5900149918https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaG1MXhtV2isbw%253D&md5=467d707d352d379c9ff427335c84d67aComplex alloy structures regarded as sphere packings. II. Analysis and classification of representative structuresFrank, F. C.; Kasper, J. S.Acta Crystallographica (1959), 12 (), 483-99CODEN: ACCRA9; ISSN:0365-110X.cf. C.A. 52, 8670d. The general principles and properties deduced previously for the class of alloy structures with triangulated co.ovrddot.ordination polyhedra, are applied in an analysis and classification of representative structures. In the main, the analysis deals with the nature of layers and how they can be stacked and with the nature of the major skeletons. Many hypothetical structures resulting from the analysis are listed, and procedures are given for predicting other structure types. The relation between alloy structures and inert gas hydrates is discussed.
- 19Bonneau, C.; O’Keeffe, M. Intermetallic Crystal Structures as Foams. Beyond Frank–Kasper. Inorg. Chem. 2015, 54 (3), 808– 814, DOI: 10.1021/ic5017966There is no corresponding record for this reference.
- 20Sikirić, M. D.; Delgado-Friedrichs, O.; Deza, M. Space Fullerenes: A Computer Search for New Frank–Kasper Structures. Acta Crystallogr., Sect. A: Found. Crystallogr. 2010, 66 (5), 602– 615, DOI: 10.1107/S0108767310022932There is no corresponding record for this reference.
- 21Kamb, B. A Clathrate Crystalline Form of Silica. Science 1965, 148 (3667), 232– 234, DOI: 10.1126/science.148.3667.232There is no corresponding record for this reference.
- 22Gies, H. Studies on Clathrasils. III.*: Crystal Structure of Melanophlogite, a Natural Clathrate Compound of Silica**. Z. Kristallogr. - Cryst. Mater. 1983, 164 (3–4), 247– 257, DOI: 10.1524/zkri.1983.164.3-4.247There is no corresponding record for this reference.
- 23Momma, K.; Ikeda, T.; Nishikubo, K.; Takahashi, N.; Honma, C.; Takada, M.; Furukawa, Y.; Nagase, T.; Kudoh, Y. New Silica Clathrate Minerals That Are Isostructural with Natural Gas Hydrates. Nat. Commun. 2011, 2 (1), 196 DOI: 10.1038/ncomms119623https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC3M7pslyluw%253D%253D&md5=5343e64269b2353d65f81786b5ed5834New silica clathrate minerals that are isostructural with natural gas hydratesMomma Koichi; Ikeda Takuji; Nishikubo Katsumi; Takahashi Naoki; Honma Chibune; Takada Masayuki; Furukawa Yoshihiro; Nagase Toshiro; Kudoh YasuhiroNature communications (2011), 2 (), 196 ISSN:.Silica clathrate compounds (clathrasils) and clathrate hydrates are structurally analogous because both materials have framework structures with cage-like voids occupied by guest species. The following three structural types of clathrate hydrates are recognized in nature: cubic structure I (sI); cubic structure II (sII); and hexagonal structure H (sH). In contrast, only one naturally occurring silica clathrate mineral, melanophlogite (sI-type framework), has been found to date. Here, we report the discovery of two new silica clathrate minerals that are isostructural with sII and sH hydrates and contain hydrocarbon gases. Geological and mineralogical observations show that these silica clathrate minerals are traces of low-temperature hydrothermal systems at convergent plate margins, which are the sources of thermogenic natural gas hydrates. Given the widespread occurrence of submarine hydrocarbon seeps, silica clathrate minerals are likely to be found in a wide range of marine sediments.
- 24Sloan, E. D. Fundamental Principles and Applications of Natural Gas Hydrates. Nature 2003, 426 (6964), 353– 359, DOI: 10.1038/nature0213524https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXptVOitLk%253D&md5=5009d19b104518ee0fd248dbbf2a72a7Fundamental principles and applications of natural gas hydratesSloan, E. DendyNature (London, United Kingdom) (2003), 426 (6964), 353-363CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)Natural gas hydrates are solid, non-stoichiometric compds. of small gas mols. and water. They form when the constituents come into contact at low temp. and high pressure. The phys. properties of these compds., most notably that they are non-flowing cryst. solids that are denser than typical fluid hydrocarbons and that the gas mols. they contain are effectively compressed, give rise to numerous applications in the broad areas of energy and climate effects. In particular, they have an important bearing on flow assurance and safety issues in oil and gas pipelines, they offer a largely unexploited means of energy recovery and transportation, and they could play a significant role in past and future climate change.
- 25Kirchner, M. T.; Boese, R.; Billups, W. E.; Norman, L. R. Gas Hydrate Single-Crystal Structure Analyses. J. Am. Chem. Soc. 2004, 126 (30), 9407– 9412, DOI: 10.1021/ja049247c25https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXlsFKrsrc%253D&md5=a7b01b53e54422b882ee9a87a2d2236bGas Hydrate Single-Crystal Structure AnalysesKirchner, Michael T.; Boese, Roland; Billups, W. Edward; Norman, Lewis R.Journal of the American Chemical Society (2004), 126 (30), 9407-9412CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)The 1st single-crystal diffraction studies on methane, propane, methane/propane, and adamantane gas hydrates SI, SII , and SH were performed. To circumvent the problem of very slow crystal growth, a novel technique of in situ cocrystn. of gases and liqs. resulting in oligocryst. material in a capillary was developed. With special data treatment, termed oligo diffractometry, structural data of the gas hydrates of methane, acetylene, propane, a propane/ethanol/methane-mixt. and an adamantane/methane-mixt. were obtained. Cell parameters are in accord with reported values. Host network and guest are subject to extensive disorder, reducing the reliability of structural information. Most cages are fully occupied by a guest mol. with the exception of the dodecahedral cage in the acetylene hydrate which is only filled to 60%. For adamantane in the icosahedral cage a disordered model is proposed.
- 26Pouchard, M.; Cros, C. The Early Development of Inorganic Clathrates. In The Physics and Chemistry of Inorganic Clathrates; Nolas, G. S., Ed.; Springer Netherlands: Dordrecht, 2014; Vol. 199, pp 1– 33.There is no corresponding record for this reference.
- 27Kasper, J. S.; Hagenmuller, P.; Pouchard, M.; Cros, C. Clathrate Structure of Silicon Na8 Si46 and Nax Si136 (x < 11). Science 1965, 150 (3704), 1713– 1714, DOI: 10.1126/science.150.3704.1713There is no corresponding record for this reference.
- 28Aydemir, U.; Akselrud, L.; Carrillo-Cabrera, W.; Candolfi, C.; Oeschler, N.; Baitinger, M.; Steglich, F.; Grin, Y. BaGe 5 : A New Type of Intermetallic Clathrate. J. Am. Chem. Soc. 2010, 132 (32), 10984– 10985, DOI: 10.1021/ja104197c28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXpsVWltb8%253D&md5=3ee7068e3514453e86b2a64b581baed3BaGe5: A New Type of Intermetallic ClathrateAydemir, Umut; Akselrud, Lev; Carrillo-Cabrera, Wilder; Candolfi, Christophe; Oeschler, Niels; Baitinger, Michael; Steglich, Frank; Grin, YuriJournal of the American Chemical Society (2010), 132 (32), 10984-10985CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)BaGe5 constitutes a new type of intermetallic clathrate obtained by decompn. of clathrate-I Ba8Ge43.box.3 at low temps. The crystal structure consists of characteristic layers interconnected by covalent bonds. BaGe5 is a semiconducting Zintl phase.
- 29He, Y.; Sui, F.; Kauzlarich, S. M.; Galli, G. Si-Based Earth Abundant Clathrates for Solar Energy Conversion. Energy Environ. Sci. 2014, 7 (8), 2598– 2602, DOI: 10.1039/C4EE00256C29https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXht1CltLzJ&md5=c0a832abf8e91dd06e15a036f09154d2Si-based Earth abundant clathrates for solar energy conversionHe, Yuping; Sui, Fan; Kauzlarich, Susan M.; Galli, GiuliaEnergy & Environmental Science (2014), 7 (8), 2598-2602CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)We synthesized a Si-based clathrate, composed entirely of Earth abundant elements, and using ab initio calcns. and spectroscopic and Hall mobility measurement showed that it is a promising material for solar energy conversion. We found that the type-I clathrate K8Al8Si38 exhibits a quasi-direct band gap of ∼1.0 eV, which may be tuned to span the IR and visible range by strain engineering. We also found that upon light absorption, excited electron and hole states are spatially sepd. in the material, with low probability of charge recombination. Finally, we computed and measured electron and hole mobilities and obtained values much superior to those of a-Si and approx. 6 to 10 and 10 to 13 time smaller than those of cryst. Si.
- 30Sui, F.; He, H.; Bobev, S.; Zhao, J.; Osterloh, F. E.; Kauzlarich, S. M. Synthesis, Structure, Thermoelectric Properties, and Band Gaps of Alkali Metal Containing Type I Clathrates: A 8 Ga 8 Si 38 (A = K, Rb, Cs) and K 8 Al 8 Si 38. Chem. Mater. 2015, 27 (8), 2812– 2820, DOI: 10.1021/cm504436vThere is no corresponding record for this reference.
- 31Luo, M.-B.; Chen, L.-J.; Huang, S.-L.; Zhou, X.; Chen, E.-X.; Lin, Q. Zeolite Analogues Based on Oxysulfidometalate Supertetrahedral Clusters via Coulombic Interactions. Inorg. Chem. Front. 2023, 10, 3224– 3229, DOI: 10.1039/D3QI00360DThere is no corresponding record for this reference.
- 32Klarreich, E. G. Foams and Honeycombs: For centuries, the precise architecture of soap foams has been a source of wonder to children and a challenge to mathematicians. Am. Sci. 2000, 88, 152– 161There is no corresponding record for this reference.
- 33Boomsma, K.; Poulikakos, D.; Ventikos, Y. Simulations of flow through open cell metal foams using an idealized periodic cell structures. Int. J. Heat Fluid Flow 2003, 24, 825– 834, DOI: 10.1016/j.ijheatfluidflow.2003.08.002There is no corresponding record for this reference.
- 34Ball, P. Beijing Bubbles. Nature 2007, 448 (7151), 256, DOI: 10.1038/448256aThere is no corresponding record for this reference.
- 35Chen, Y.; Takeya, S.; Sum, A. K. Topological Dual and Extended Relations between Networks of Clathrate Hydrates and Frank-Kasper Phases. Nat. Commun. 2023, 14 (1), 596 DOI: 10.1038/s41467-023-36242-4There is no corresponding record for this reference.
- 36Hudson, S. D.; Jung, H.-T.; Percec, V.; Cho, W.-D.; Johansson, G.; Ungar, G.; Balagurusamy, V. S. K. Direct Visualization of Individual Cylindrical and Spherical Supramolecular Dendrimers. Science 1997, 278 (5337), 449– 452, DOI: 10.1126/science.278.5337.44936https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2sXmslKjtrY%253D&md5=7c9bbc5ae7ff97c499aacea519edb208Direct visualization of individual cylindrical and spherical supramolecular dendrimersHudson, S. D.; Jung, H.-T.; Percec, V.; Cho, W.-D.; Johansson, G.; Ungar, G.; Balagurusamy, V. S. K.Science (Washington, D. C.) (1997), 278 (5337), 449-452CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Electron microscopy methods have been used to visualize individual spherical and cylindrical supramol. dendrimers, providing definitive confirmation of the structure suggested by previous x-ray diffraction anal. that assumed a micro-segregated model. These dendrimers are self-assembled self-organized, and aligned spontaneously and simultaneously in hexagonal columnar or cubic thermotropic liq.-crystal phases with high uniformity. Homeotropic and planar ordering of the hexagonal columnar liq. crystal was precisely controlled by a variety of surfaces. The stiffness of these cylinders was evaluated by examg. their planar texture and its defects.
- 37Percec, V.; Cho, W.-D.; Möller, M.; Prokhorova, S. A.; Ungar, G.; Yeardley, D. J. P. Design and Structural Analysis of the First Spherical Monodendron Self-Organizable in a Cubic Lattice. J. Am. Chem. Soc. 2000, 122 (17), 4249– 4250, DOI: 10.1021/ja994340037https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3cXitlyquro%253D&md5=a1f806f7cf80dd67e5186c62783329a7Design and Structural Analysis of the First Spherical Monodendron Self-Organizable in a Cubic LatticePercec, Virgil; Cho, Wook-Dong; Moeller, Martin; Prokhorova, Svetlana A.; Ungar, Goran; Yeardley, Duncan J. P.Journal of the American Chemical Society (2000), 122 (17), 4249-4250CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)The design, synthesis (divergent approach with Me 3,4,5-trihydroxybenzoate), and structural anal. (by x-ray diffraction) of spherical functional monodendrons of the type (3,4-(3,4,5)n-1)12GnX (n (generation) = 1-5, and X = CH2OH, COOH, or CO2CH3) that self-organizes in a cubic Pm3n lattice is reported. The prepd. monodendrons were addnl. examd. by differential scanning calorimetry, thermal optical polarized microscopy, and scanning force microscopy. The lattice parameters, the diam. of supramol. or mol. dendritic sphere, the no. of monodendrons that self-assemble into a sphere, and the theor. molar mass of the monodendrons were detd.
- 38Ungar, G.; Liu, Y.; Zeng, X.; Percec, V.; Cho, W.-D. Giant Supramolecular Liquid Crystal Lattice. Science 2003, 299 (5610), 1208– 1211, DOI: 10.1126/science.107884938https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXht12jtLc%253D&md5=8ca2656f954ef3d899050785d222e586Giant Supramolecular Liquid Crystal LatticeUngar, Goran; Liu, Yongsong; Zeng, Xiangbing; Percec, Virgil; Cho, Wook-DongScience (Washington, DC, United States) (2003), 299 (5610), 1208-1211CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Self-organized supramol. org. nanostructures have potential applications that include mol. electronics, photonics, and precursors for nanoporous catalysts. Accordingly, understanding how self-assembly is controlled by mol. architecture will enable the design of increasingly complex structures. The authors report a liq. crystal (LC) phase with a tetragonal three-dimensional unit cell contg. 30 globular supramol. dendrimers, each of which is self-assembled from 12 dendron (tree-like) mols., for the compds. described here. The present structure is one of the most complex LC phases yet discovered. A model explaining how spatial arrangement of self-assembled dendritic aggregates depends on mol. architecture and temp. is proposed.
- 39Percec, V.; Peterca, M.; Dulcey, A. E.; Imam, M. R.; Hudson, S. D.; Nummelin, S.; Adelman, P.; Heiney, P. A. Hollow Spherical Supramolecular Dendrimers. J. Am. Chem. Soc. 2008, 130 (39), 13079– 13094, DOI: 10.1021/ja803470339https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXhtVOqtLvN&md5=0025780b59b8620d5999c23a572a4b71Hollow Spherical Supramolecular DendrimersPercec, Virgil; Peterca, Mihai; Dulcey, Andres E.; Imam, Mohammad R.; Hudson, Steven D.; Nummelin, Sami; Adelman, Peter; Heiney, Paul A.Journal of the American Chemical Society (2008), 130 (39), 13079-13094CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)The synthesis of a library contg. 12 conical dendrons that self-assemble into hollow spherical supramol. dendrimers is reported. The design principles for this library were accessed by development of a method that allows the identification of hollow spheres, followed by structural and retrostructural anal. of their Pm‾3n cubic lattice. The first hollow spherical supramol. dendrimer was made by replacing the tapered dendron, from the previously reported tapered dendritic dipeptide that self-assembled into helical pores, with its constitutional isomeric conical dendron. This strategy generated a conical dendritic dipeptide that self-assembled into a hollow spherical supramol. dendrimer that self-organizes in a Pm‾3n cubic lattice. Other examples of hollow spheres were assembled from conical dendrons without a dipeptide at their apex. These are conical dendrons originated from tapered dendrons contg. addnl. benzyl ether groups at their apex. The inner part of the hollow sphere assembled from the dipeptide resembles the path of a spherical helix or loxodrome and, therefore, is chiral. The spheres assembled from other conical dendrons are nonhelical, even when they contain stereocenters on the alkyl groups from their periphery. Functionalization of the apex of the conical dendrons with diethylene glycol allowed the encapsulation of LiOTf and RbOTf in the center of the hollow sphere. These expts. showed that hollow spheres function as supramol. dendritic capsules and therefore are expected to display functions complementary to those of other related mol. and supramol. structures.
- 40Bates, M. W.; Lequieu, J.; Barbon, S. M.; Lewis, R. M.; Delaney, K. T.; Anastasaki, A.; Hawker, C. J.; Fredrickson, G. H.; Bates, C. M. Stability of the A15 Phase in Diblock Copolymer Melts. Proc. Natl. Acad. Sci. U.S.A. 2019, 116 (27), 13194– 13199, DOI: 10.1073/pnas.190012111640https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXht1ykt7jI&md5=4a1ba54de2f345473cc0dd3fb57e218bStability of the A15 phase in diblock copolymer meltsBates, Morgan W.; Lequieu, Joshua; Barbon, Stephanie M.; Lewis, Ronald M., III; Delaney, Kris T.; Anastasaki, Athina; Hawker, Craig J.; Fredrickson, Glenn H.; Bates,, Christopher M.Proceedings of the National Academy of Sciences of the United States of America (2019), 116 (27), 13194-13199CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)The self-assembly of block polymers into well-ordered nanostructures underpins their utility across fundamental and applied polymer science, yet only a handful of equil. morphologies are known with the simplest AB-type materials. Here, we report the discovery of the A15 sphere phase in single-component diblock copolymer melts comprising poly(dodecyl acrylate)-block-poly(lactide). A systematic exploration of phase space revealed that A15 forms across a substantial range of minority lactide block vol. fractions (fL = 0.25 - 0.33) situated between the σ-sphere phase and hexagonally close-packed cylinders. SCF theory rationalizes the thermodn. stability of A15 as a consequence of extreme conformational asymmetry. The exptl. obsd. A15-disorder phase transition is not captured using mean-field approxns. but instead arises due to compn. fluctuations as evidenced by fully fluctuating field-theoretic simulations. This combination of expts. and field-theoretic simulations provides rational design rules that can be used to generate unique, polymer-based mesophases through self-assembly.
- 41Watanabe, M.; Asai, Y.; Suzuki, J.; Takano, A.; Matsushita, Y. Frank-Kasper A15 Phase Formed in ABn Block-Graft Copolymers with Large Numbers of Graft Chains. Macromolecules 2020, 53 (22), 10217– 10224, DOI: 10.1021/acs.macromol.0c0109741https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXit1SgtbnM&md5=61871cdf52f2faa1933af1119d88a53bFrank-Kasper A15 Phase Formed in ABn Block-Graft Copolymers with Large Numbers of Graft ChainsWatanabe, Momoka; Asai, Yusuke; Suzuki, Jiro; Takano, Atsushi; Matsushita, YushuMacromolecules (Washington, DC, United States) (2020), 53 (22), 10217-10224CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)Microphase-sepd. structures of a series of ABn block-graft copolymers were studied by transmission electron microscopy (TEM) coupled with small-angle X-ray scattering (SAXS). Five block-graft copolymers composed of the same polystyrene (S) backbone having polyisoprene (I) grafts with different chain lengths, wherein the nos. of grafts are almost const. (38 on av.), were synthesized by living anionic polymns., resulting in coverage of the polystyrene compn. range 0.32 ≤ φS ≤ 0.91. It was confirmed from the TEM observation that three low φS samples with φS of 0.32, 0.37, and 0.39 show complex spherical structures, while the sample with an φS of 0.57 reveals a hexagonal assembly of hexagonal rods of S in an I matrix, and the sample with φS of 0.91 exhibits inverse morphologies having rods of I in an S matrix. From detailed TEM and SAXS investigation combined with simulations, it has been found that the spherical structures formed from the samples with φS of 0.32 and 0.37 are both confirmed to have the structural feature of the Frank-Kasper A15 phase, which possesses the structural symmetry of the Pm3n space group.
- 42Montis, R.; Fusaro, L.; Falqui, A.; Hursthouse, M. B.; Tumanov, N.; Coles, S. J.; Threlfall, T. L.; Horton, P. N.; Sougrat, R.; Lafontaine, A.; Coquerel, G.; Rae, A. D. Complex Structures Arising from the Self-Assembly of a Simple Organic Salt. Nature 2021, 590 (7845), 275– 278, DOI: 10.1038/s41586-021-03194-y42https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXjslKnsrc%253D&md5=11b758eb57af740e61b8dc421f7460dfComplex structures arising from the self-assembly of a simple organic saltMontis, Riccardo; Fusaro, Luca; Falqui, Andrea; Hursthouse, Michael B.; Tumanov, Nikolay; Coles, Simon J.; Threlfall, Terry L.; Horton, Peter N.; Sougrat, Rachid; Lafontaine, Anais; Coquerel, Gerard; Rae, A. DavidNature (London, United Kingdom) (2021), 590 (7845), 275-278CODEN: NATUAS; ISSN:0028-0836. (Nature Research)Mol. self-assembly is the spontaneous assocn. of simple mols. into larger and ordered structures1. It is the basis of several natural processes, such as the formation of colloids, crystals, proteins, viruses and double-helical DNA2. Mol. self-assembly has inspired strategies for the rational design of materials with specific chem. and phys. properties3, and is one of the most important concepts in supramol. chem. Although mol. self-assembly has been extensively investigated, understanding the rules governing this phenomenon remains challenging. Here we report on a simple hydrochloride salt of fampridine that crystallizes as four different structures, two of which adopt unusual self-assemblies consisting of polyhedral clusters of chloride and pyridinium ions. These two structures represent Frank-Kasper (FK) phases of a small and rigid org. mol. Although discovered in metal alloys4,5 more than 60 years ago, FK phases have recently been obsd. in several classes of supramol. soft matter6-11 and in gold nanocrystal superlattices12 and remain the object of recent discoveries13. In these systems, atoms or spherical assemblies of mols. are packed to form polyhedra with coordination nos. 12, 14, 15 or 16. The two FK structures reported here crystallize from a dense liq. phase and show a complexity that is generally not obsd. in small rigid org. mols. Investigation of the precursor dense liq. phase by cryogenic electron microscopy reveals the presence of spherical aggregates with sizes ranging between 1.5 and 4.6 nm. These structures, together with the exptl. procedure used for their prepn., invite interesting speculation about their formation and open different perspectives for the design of org. cryst. materials.
- 43Kim, S. A.; Jeong, K.-J.; Yethiraj, A.; Mahanthappa, M. K. Low-Symmetry Sphere Packings of Simple Surfactant Micelles Induced by Ionic Sphericity. Proc. Natl. Acad. Sci. U.S.A. 2017, 114 (16), 4072– 4077, DOI: 10.1073/pnas.170160811443https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXlsV2ntr8%253D&md5=793e22c1a4dcd276a815bb1ab3e4f973Low-symmetry sphere packings of simple surfactant micelles induced by ionic sphericityKim, Sung A.; Jeong, Kyeong-Jun; Yethiraj, Arun; Mahanthappa, Mahesh K.Proceedings of the National Academy of Sciences of the United States of America (2017), 114 (16), 4072-4077CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)Supramol. self-assembly enables access to designer soft materials that typically exhibit high-symmetry packing arrangements, which optimize the interactions between their mesoscopic constituents over multiple length scales. The authors report the discovery of an ionic small mol. surfactant that undergoes H2O-induced self-assembly into spherical micelles, which pack into a previously unknown, low-symmetry lyotropic liq. cryst. Frank-Kasper σ phase. Small-angle x-ray scattering studies reveal that this complex phase is characterized by a gigantic tetragonal unit cell, in which 30 sub-2-nm quasispherical micelles of 5 discrete sizes are arranged into a tetrahedral close packing, with exceptional translational order over length scales exceeding 100 nm. Varying the relative concns. of H2O and surfactant in these lyotropic phases also triggers formation of the related Frank-Kasper A15 sphere packing as well as a common bcc. structure. Mol. dynamics simulations reveal that the symmetry breaking that drives the formation of the σ and A15 phases arises from minimization of local deviations in surfactant headgroup and counterion solvation to maintain a nearly spherical counterion atm. around each micelle, while maximizing counterion-mediated electrostatic cohesion among the ensemble of charged particles.
- 44Huang, M.; Hsu, C.-H.; Wang, J.; Mei, S.; Dong, X.; Li, Y.; Li, M.; Liu, H.; Zhang, W.; Aida, T.; Zhang, W.-B.; Yue, K.; Cheng, S. Z. D. Selective Assemblies of Giant Tetrahedra via Precisely Controlled Positional Interactions. Science 2015, 348 (6233), 424– 428, DOI: 10.1126/science.aaa242144https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXmslOntrY%253D&md5=10e120e314fe650268decdd8dd5a23b4Selective assemblies of giant tetrahedra via precisely controlled positional interactionsHuang, Mingjun; Hsu, Chih-Hao; Wang, Jing; Mei, Shan; Dong, Xuehui; Li, Yiwen; Li, Mingxuan; Liu, Hao; Zhang, Wei; Aida, Takuzo; Zhang, Wen-Bin; Yue, Kan; Cheng, Stephen Z. D.Science (Washington, DC, United States) (2015), 348 (6233), 424-428CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Self-assembly of rigid building blocks with explicit shape and symmetry is substantially influenced by the geometric factors and remains largely unexplored. The authors report the selective assembly behaviors of a class of precisely defined, nanosized giant tetrahedra constructed by placing different polyhedral oligomeric silsesquioxane (POSS) mol. nanoparticles at the vertexes of a rigid tetrahedral framework. Designed symmetry breaking of these giant tetrahedra introduces precise positional interactions and results in diverse selectively assembled, highly ordered supramol. lattices including a Frank-Kasper A15 phase, which resembles the essential structural features of certain metal alloys but at a larger length scale. These results demonstrate the power of persistent mol. geometry with balanced enthalpy and entropy in creating thermodynamically stable supramol. lattices with properties distinct from those of other self-assembling soft materials.
- 45Su, Z.; Hsu, C.-H.; Gong, Z.; Feng, X.; Huang, J.; Zhang, R.; Wang, Y.; Mao, J.; Wesdemiotis, C.; Li, T.; Seifert, S.; Zhang, W.; Aida, T.; Huang, M.; Cheng, S. Z. D. Identification of a Frank–Kasper Z Phase from Shape Amphiphile Self-Assembly. Nat. Chem. 2019, 11 (10), 899– 905, DOI: 10.1038/s41557-019-0330-x45https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhvVGgurfL&md5=942e450b5fd455f9b611e9a49aa651dfIdentification of a Frank-Kasper Z phase from shape amphiphile self-assemblySu, Zebin; Hsu, Chih-Hao; Gong, Zihao; Feng, Xueyan; Huang, Jiahao; Zhang, Ruimeng; Wang, Yu; Mao, Jialin; Wesdemiotis, Chrys; Li, Tao; Seifert, Soenke; Zhang, Wei; Aida, Takuzo; Huang, Mingjun; Cheng, Stephen Z. D.Nature Chemistry (2019), 11 (10), 899-905CODEN: NCAHBB; ISSN:1755-4330. (Nature Research)Frank-Kasper phases, a family of ordered structures formed from particles with spherical motifs, are found in a host of materials, such as metal alloys, inorg. colloids and various types of soft matter. All the exptl. obsd. Frank-Kasper phases can be constructed from the basic units of three fundamental structures called the A15, C15 and Z phases. The Z phase, typically obsd. in metal alloys, is assocd. with a relatively large vol. ratio between its constituents, and this constraint inhibits its formation in most self-assembled single-component soft-matter systems. We have assembled a series of nanosized shape amphiphiles that comprise a triphenylene core and six polyhedral oligomeric silsesquioxane cages grafted onto it through linkers to give a variety of unconventional structures, which include the Z phase. This structure was obtained through fine tuning of the linker lengths between the core and the peripheral polyhedral oligomeric silsesquioxane cages, and exhibits a relatively large vol. asymmetry between its constituent polyhedral particle motifs.
- 46Chen, C.; Poppe, M.; Poppe, S.; Wagner, M.; Tschierske, C.; Liu, F. Tetrahedral liquid-crystalline networks: an A15-like Frank-Kasper Phase based on rod-packing. Angew. Chem., Int. Ed. 2022, 61 (27), e202203447 DOI: 10.1002/anie.202203447There is no corresponding record for this reference.
- 47Lin, H.; Lee, S.; Sun, L.; Spellings, M.; Engel, M.; Glotzer, S. C.; Mirkin, C. A. Clathrate Colloidal Crystals. Science 2017, 355 (6328), 931– 935, DOI: 10.1126/science.aal391947https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXjsVCgsr8%253D&md5=801bf70967e15228884670bc0dc49f78Clathrate colloidal crystalsLin, Haixin; Lee, Sangmin; Sun, Lin; Spellings, Matthew; Engel, Michael; Glotzer, Sharon C.; Mirkin, Chad A.Science (Washington, DC, United States) (2017), 355 (6328), 931-935CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)DNA-programmable assembly was used to deliberately synthesize hundreds of different colloidal crystals spanning dozens of symmetries, but the complexity of the achieved structures has so far been limited to small unit cells. DNA-modified triangular bipyramids (∼250-nm long edge, 177-nm short edge) were assembled into clathrate architectures. Electron microscopy images revealed that ≥3 different structures form as large single-domain architectures or as multidomain materials. Ordered assemblies, isostructural to clathrates, were identified with the help of mol. simulations and geometric anal. These structures are the most sophisticated architectures made via programmable assembly, and their formation can be understood based on the shape of the nanoparticle building blocks and mode of DNA functionalization.
- 48Girard, M.; Wang, S.; Du, J. S.; Das, A.; Huang, Z.; Dravid, V. P.; Lee, B.; Mirkin, C. A.; De La Cruz, M. O. Particle Analogs of Electrons in Colloidal Crystals. Science 2019, 364 (6446), 1174– 1178, DOI: 10.1126/science.aaw823748https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhtlKqsL7M&md5=e2767780ae789f4b14ef9f93710ffcd1Particle analogs of electrons in colloidal crystalsGirard, Martin; Wang, Shunzhi; Du, Jingshan S.; Das, Anindita; Huang, Ziyin; Dravid, Vinayak P.; Lee, Byeongdu; Mirkin, Chad A.; Olvera de la Cruz, MonicaScience (Washington, DC, United States) (2019), 364 (6446), 1174-1178CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)A versatile method for the design of colloidal crystals involves the use of DNA as a particle-directing ligand. With such systems, DNA-nanoparticle conjugates are considered programmable atom equiv. (PAEs), and design rules have been devised to engineer crystn. outcomes. This work shows that when reduced in size and DNA grafting d., PAEs behave as electron equiv. (EEs), roaming through and stabilizing the lattices defined by larger PAEs, as electrons do in metals in the classical picture. This discovery defines a new property of colloidal crystals-metallicity-that is characterized by the extent of EE delocalization and diffusion. As the no. of strands increases or the temp. decreases, the EEs localize, which is structurally reminiscent of a metal-insulator transition. Colloidal crystal metallicity, therefore, provides new routes to metallic, intermetallic, and compd. phases.
- 49Wang, S.; Lee, S.; Du, J. S.; Partridge, B. E.; Cheng, H. F.; Zhou, W.; Dravid, V. P.; Lee, B.; Glotzer, S. C.; Mirkin, C. A. The Emergence of Valency in Colloidal Crystals through Electron Equivalents. Nat. Mater. 2022, 21 (5), 580– 587, DOI: 10.1038/s41563-021-01170-549https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38Xht1KqsL4%253D&md5=f453edd0c938eb145ae76fc34271fbd0The emergence of valency in colloidal crystals through electron equivalentsWang, Shunzhi; Lee, Sangmin; Du, Jingshan S.; Partridge, Benjamin E.; Cheng, Ho Fung; Zhou, Wenjie; Dravid, Vinayak P.; Lee, Byeongdu; Glotzer, Sharon C.; Mirkin, Chad A.Nature Materials (2022), 21 (5), 580-587CODEN: NMAACR; ISSN:1476-1122. (Nature Portfolio)Colloidal crystal engineering of complex, low-symmetry architectures is challenging when isotropic building blocks are assembled. Here we describe an approach to generating such structures based upon programmable atom equiv. (nanoparticles functionalized with many DNA strands) and mobile electron equiv. (small particles functionalized with a low no. of DNA strands complementary to the programmable atom equiv.). Under appropriate conditions, the spatial distribution of the electron equiv. breaks the symmetry of isotropic programmable atom equiv., akin to the anisotropic distribution of valence electrons or coordination sites around a metal atom, leading to a set of well-defined coordination geometries and access to three new low-symmetry cryst. phases. All three phases represent the first examples of colloidal crystals, with two of them having elemental analogs (body-centered tetragonal and high-pressure gallium), while the third (triple double-gyroid structure) has no known natural equiv. This approach enables the creation of complex, low-symmetry colloidal crystals that might find use in various technologies.
- 50Fang, Q.; Zhu, G.; Xue, M.; Sun, J.; Wei, Y.; Qiu, S.; Xu, R. A Metal–Organic Framework with the Zeolite MTN Topology Containing Large Cages of Volume 2.5 nm3. Angew. Chem., Int. Ed. 2005, 44 (25), 3845– 3848, DOI: 10.1002/anie.200462260There is no corresponding record for this reference.
- 51Férey, G.; Serre, C.; Mellot-Draznieks, C.; Millange, F.; Surblé, S.; Dutour, J.; Margiolaki, I. A Hybrid Solid with Giant Pores Prepared by a Combination of Targeted Chemistry, Simulation, and Powder Diffraction. Angew. Chem., Int. Ed. 2004, 43 (46), 6296– 6301, DOI: 10.1002/anie.20046059251https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXhtFWrtL7J&md5=7200674db845103909fe0af6ea2f7e01Molecular modeling: A hybrid solid with giant pores prepared by a combination of targeted chemistry, simulation, and powder diffractionFerey, Gerard; Serre, Christian; Mellot-Draznieks, Caroline; Millange, Franck; Surble, Suzy; Dutour, Julien; Margiolaki, IreneAngewandte Chemie, International Edition (2004), 43 (46), 6296-6301CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)The assocn. of a chromium(III) trimeric building unit and 1,3,5-benzenetricarboxylate led to the powd. solid MIL-100. Simulations provided a crystal structure soln., which matched the exptl. powder XRD pattern. This unique simulation/diffraction combination allowed the structure detn. of a giant-pore solid with a zeotype architecture, built up from hybrid supertetrahedra.
- 52Férey, G.; Mellot-Draznieks, C.; Serre, C.; Millange, F.; Dutour, J.; Surblé, S.; Margiolaki, I. A Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area. Science 2005, 309 (5743), 2040– 2042, DOI: 10.1126/science.111627552https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXhtVWntL3E&md5=6313e7e95b0edca92bb34df3f0c9752dA Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface AreaFerey, G.; Mellot-Draznieks, C.; Serre, C.; Millange, F.; Dutour, J.; Surble, S.; Margiolaki, I.Science (Washington, DC, United States) (2005), 309 (5743), 2040-2042CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)We combined targeted chem. and computational design to create a crystal structure for porous chromium terephthalate, MIL-101, with very large pore sizes and surface area. Its zeotype cubic structure has a giant cell vol. (∼702,000 cubic angstroms), a hierarchy of extra-large pore sizes (∼30 to 34 angstroms), and a Langmuir surface area for N2 of ∼5900 ± 300 square meters per g. Beside the usual properties of porous compds., this solid has potential as a nanomold for monodisperse nanomaterials, as illustrated here by the incorporation of Keggin polyanions within the cages.
- 53Park, Y. K.; Choi, S. B.; Kim, H.; Kim, K.; Won, B.; Choi, K.; Choi, J.; Ahn, W.; Won, N.; Kim, S.; Jung, D. H.; Choi, S.; Kim, G.; Cha, S.; Jhon, Y. H.; Yang, J. K.; Kim, J. Crystal Structure and Guest Uptake of a Mesoporous Metal–Organic Framework Containing Cages of 3.9 and 4.7 nm in Diameter. Angew. Chem., Int. Ed. 2007, 46 (43), 8230– 8233, DOI: 10.1002/anie.20070232453https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXhtlCkur7L&md5=e07d391f92e24f51a87523b24f935fcaCrystal structure and guest uptake of a mesoporous metal-organic framework containing cages of 3.9 and 4.7 nm in diameterPark, Young Kwan; Choi, Sang Beom; Kim, Hyunuk; Kim, Kimoon; Won, Byoung-Ho; Choi, Kihang; Choi, Jung-Sik; Ahn, Wha-Seung; Won, Nayoun; Kim, Sungjee; Jung, Dong, Hyun; Choi, Seung-Hoon; Kim, Ghyung-Hwa; Cha, Sun-Shin; Jhon, Young Ho; Yang, Jin KukAngewandte Chemie, International Edition (2007), 46 (43), 8230-8233CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)A new mesoporous metal-org. (MOF) framework that is mainly composed of Tb3+ ions and tripodal 1,3,5-triazine-2,4,6-tri-p-benzoate ligands has cages of 3.9 and 4.7 nm in diam. The evacuated framework is robust and can accommodate gases (N2, CO2) or ferrocene mols., as verified by gas-sorption measurements and luminescence studies.
- 54Kang, Y.; Wang, F.; Zhang, J.; Bu, X. Luminescent MTN -Type Cluster–Organic Framework with 2.6 nm Cages. J. Am. Chem. Soc. 2012, 134 (43), 17881– 17884, DOI: 10.1021/ja308801n54https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhsFSgs7fP&md5=7ebf5d1388492a8d4d9c86f3a26602ceLuminescent MTN-Type Cluster-Organic Framework with 2.6 nm CagesKang, Yao; Wang, Fei; Zhang, Jian; Bu, XianhuiJournal of the American Chemical Society (2012), 134 (43), 17881-17884CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)From a basic tetrahedral Cu4I4 cluster, a new MTN-type cluster-org. framework [Cu4I4(dabco)2]n (COZ-1) contg. giant 64512 and 512 cages was successfully constructed. The 64512 cage has an inner diam. of 2.6 nm and a large pore vol. of 9.2 nm3; these tetrahedral Cu4I4 clusters with bulky size offer new opportunities for not only the formation of 4-connected zeotype structures but also the integration of porosity and photoluminescent properties from both the cluster and the framework.
- 55Thorp-Greenwood, F. L.; Kulak, A. N.; Hardie, M. J. Three-Dimensional Silver-Dabco Coordination Polymers with Zeolitic or Three-Connected Topology. Cryst. Growth Des. 2014, 14 (11), 5361– 5365, DOI: 10.1021/cg501231v55https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhsl2hsLfO&md5=e8fd9d3d6bca43d21f308f471bd69de8Three-Dimensional Silver-dabco Coordination Polymers with Zeolitic or Three-Connected TopologyThorp-Greenwood, Flora L.; Kulak, Alexander N.; Hardie, Michaele J.Crystal Growth & Design (2014), 14 (11), 5361-5365CODEN: CGDEFU; ISSN:1528-7483. (American Chemical Society)The simple linear linking ligand diazabicyclo[2.2.2]octane (dabco) combines with silver(I) to form three-dimensional (3D) coordination polymers which have either a zeolitic mtn topol. structure or a (10,3)-b ths network according to the counteranion used. The tetrahedral anions BF4- or ReO4- promote formation of [Ag(dabco)2]·X, which has a 3D four-connected mtn framework of fused 512 and 64512 cages, and the material shows modest absorption of iodine. The bulky anion [Co(C2B9H11)2]- and an excess of dabco promote formation of complex [Ag2(dabco)3(CH3CN)2]·2[Co(C2B9H11)2] with a three-connected (10,3)-b network, while use of 1 equiv of dabco gives a previously reported [Ag(dabco)]·[Co(C2B9H11)2], which has a one-dimensional coordination chain structure.
- 56Park, K. S.; Ni, Z.; Côté, A. P.; Choi, J. Y.; Huang, R.; Uribe-Romo, F. J.; Chae, H. K.; O’Keeffe, M.; Yaghi, O. M. Exceptional Chemical and Thermal Stability of Zeolitic Imidazolate Frameworks. Proc. Natl. Acad. Sci. U.S.A. 2006, 103 (27), 10186– 10191, DOI: 10.1073/pnas.060243910356https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XntlKjtbo%253D&md5=c28cd5862d4765fe4e4937195f5bb4dfExceptional chemical and thermal stability of zeolitic imidazolate frameworksPark, Kyo Sung; Ni, Zheng; Cote, Adrien P.; Choi, Jae Yong; Huang, Rudan; Uribe-Romo, Fernando J.; Chae, Hee K.; O'Keeffe, Michael; Yaghi, Omar M.Proceedings of the National Academy of Sciences of the United States of America (2006), 103 (27), 10186-10191CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)Twelve zeolitic imidazolate frameworks (ZIFs; termed ZIF-1 to -12) were synthesized as crystals by copolymn. of either Zn(II) (ZIF-1 to -4, -6 to -8, and -10 to -11) or Co(II) (ZIF-9 and -12) with imidazolate-type links. The ZIF crystal structures are based on the nets of seven distinct aluminosilicate zeolites: tetrahedral Si(Al) and the bridging O are replaced with transition metal ion and imidazolate link, resp. One example of mixed-coordination imidazolate of Zn(II) and In(III) (ZIF-5) based on the garnet net is reported. Study of the gas adsorption and thermal and chem. stability of two prototypical members, ZIF-8 and -11, demonstrated their permanent porosity (Langmuir surface area = 1,810 m2/g), high thermal stability (up to 550°), and remarkable chem. resistance to boiling alk. H2O and org. solvents.
- 57O’Keeffe, M.; Adams, G. B.; Sankey, O. F. Duals of Frank-Kasper Structures as C, Si and Ge Clathrates: Energetics and Structure. Philos. Mag. Lett. 1998, 78 (1), 21– 28, DOI: 10.1080/095008398178219There is no corresponding record for this reference.
- 58Thomson, W. On the division of space with minimum partitional area. Acta Math. 1887, 11, 121– 134, DOI: 10.1007/BF02612322There is no corresponding record for this reference.
- 59Gray, J. Parsimonious Polyhedra. Nature 1994, 367, 598– 599, DOI: 10.1038/367598a0There is no corresponding record for this reference.
- 60Weaire, D.; Phelan, R. A Counter-Example to Kelvin’s Conjecture on Minimal Surfaces. Philos. Mag. Lett. 1994, 69 (2), 107– 110, DOI: 10.1080/0950083940824157760https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2cXktFyksL0%253D&md5=0168c197b0e37ea4abe7f673b900cb07A counter-example to Kelvin's conjecture on minimal surfacesWeaire, D.; Phelan, R.Philosophical Magazine Letters (1994), 69 (2), 107-10CODEN: PMLEEG; ISSN:0950-0839.Kelvin's conjecture, that a bcc. arrangement of his minimal tetrakaidecahedron divides space into equal cells of min. surface area, has stood for over one hundred years. The authors have found a counter-example, in the form of a structure analogous to that of some clathrate compds. and also related to the β-tungsten structure. Its surface area is approx. 0.3% less than that of Kelvin's structure.
- 61Gabbrielli, R.; Meagher, A. J.; Weaire, D.; Brakke, K. A.; Hutzler, S. An Experimental Realization of the Weaire–Phelan Structure in Monodisperse Liquid Foam. Philos. Mag. Lett. 2012, 92 (1), 1– 6, DOI: 10.1080/09500839.2011.64589861https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhtFWrtbk%253D&md5=ad54919fd4ace7e183cf17a8cdaf2e14An experimental realization of the Weaire-Phelan structure in monodisperse liquid foamGabbrielli, Ruggero; Meagher, Aaron J.; Weaire, Denis; Brakke, Kenneth A.; Hutzler, StefanPhilosophical Magazine Letters (2012), 92 (1), 1-6CODEN: PMLEEG; ISSN:0950-0839. (Taylor & Francis Ltd.)The Weaire-Phelan (WP) structure is the lowest energy structure known of an ideal monodisperse foam in the dry limit. To date, it has not been realized in the lab. Instead Lord Kelvin's 1887 structure, which it supplanted in 1994, has repeatedly been found in attempts to produce an ordered structure. This paradox is attributable to the flat walls of the containers used, with which the Kelvin structure is more compatible. Accordingly, we have fabricated a patterned mold whose faceted walls conform to the WP geometry, and thereby succeeded in inducing the formation of perfect crystals of the WP structure. Foam samples consisted of approx. 1500 bubbles. Vibrations favored crystn.
- 62Bacsa, J.; Less, R. J.; Skelton, H. E.; Soracevic, Z.; Steiner, A.; Wilson, T. C.; Wood, P. T.; Wright, D. S. Assembly of the First Fullerene-Type Metal–Organic Frameworks Using a Planar Five-Fold Coordination Node. Angew. Chem., Int. Ed. 2011, 50 (36), 8279– 8282, DOI: 10.1002/anie.20110278362https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXptlaksrc%253D&md5=d015749e01eaf82d767ed559282a6ec3Assembly of the First Fullerene-Type Metal-Organic Frameworks Using a Planar Five-Fold Coordination NodeBacsa, John; Less, Robert J.; Skelton, Helen E.; Soracevic, Zlatko; Steiner, Alexander; Wilson, Thomas C.; Wood, Paul T.; Wright, Dominic S.Angewandte Chemie, International Edition (2011), 50 (36), 8279-8282, S8279/1-S8279/4CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)A fullerene-type metal-org. framework was constructed using the planar pentacyanocyclopentadienide ligand. Recrystn. of sodium pentacyanocyclopentadienide in MeNO2 by vapor diffusion of Et2O resulted in the formation of the metal-org. framework complex [Na46(L)48][Na2]·xMeNO2·yEt2O which was structurally characterized.
- 63Zhang, W.; Wang, K.; Li, J.; Lin, Z.; Song, S.; Huang, S.; Liu, Y.; Nie, F.; Zhang, Q. Stabilization of the Pentazolate Anion in a Zeolitic Architecture with Na20 N60 and Na24 N60 Nanocages. Angew. Chem., Int. Ed. 2018, 57 (10), 2592– 2595, DOI: 10.1002/anie.201710602There is no corresponding record for this reference.
- 64Schlenker, J. L.; Dwyer, F. G.; Jenkins, E. E.; Rohrbaugh, W. J.; Kokotailo, G. T.; Meier, W. M. Crystal Structure of a Synthetic High Silica Zeolite─ZSM-39. Nature 1981, 294 (5839), 340– 342, DOI: 10.1038/294340a0There is no corresponding record for this reference.
- 65Baerlocher, C.; McCusker, L. Database of zeolite structures 2017 http://www.izastructure.org/databases/.There is no corresponding record for this reference.
- 66Gómez-Gualdrón, D. A.; Cólon, Y. J.; Zhang, X.; Wang, T. C.; Chen, Y.-S.; Hupp, J. T.; Yildrim, T.; Farha, O. K.; Zhang, J.; Snurr, R. Q. Evaluating Topologically Diverse Metal–Organic Frameworks for Cryo-Adsorbed Hydrogen Storage. Energy Environ. Sci. 2016, 9 (10), 3279– 3289, DOI: 10.1039/C6EE02104B66https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhsVykt77O&md5=9793b81106ea8ffaaf36f07cc9f60b10Evaluating topologically diverse metal-organic frameworks for cryo-adsorbed hydrogen storageGomez-Gualdron, Diego A.; Colon, Yamil J.; Zhang, Xu; Wang, Timothy C.; Chen, Yu-Sheng; Hupp, Joseph T.; Yildirim, Taner; Farha, Omar K.; Zhang, Jian; Snurr, Randall Q.Energy & Environmental Science (2016), 9 (10), 3279-3289CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)Metal-org. frameworks (MOFs) are porous materials synthesized by combining inorg. and org. mol. building blocks into cryst. networks of distinct topologies. Due to the combinatorial possibilities, there are millions of possible MOF structures. Aiming to exploit their exceptional tunability, surface areas and pore vols., researchers have investigated MOFs for storage of gaseous fuels such as hydrogen for over a decade, but a suitable MOF to store hydrogen at ambient conditions has not yet been found. Here, we sought to rapidly det. the viability of using MOFs for hydrogen storage at recently proposed, cryogenic operating conditions. We constructed a large and structurally diverse set of 13 512 potential MOF structures based on 41 different topologies and used mol. simulation to det. MOF hydrogen deliverable capacities between 100 bar/77 K and 5 bar/160 K. The highest volumetric deliverable capacity was 57 g L-1 of MOF, which surpasses the 37 g L-1 of tank of the incumbent technol. (compressing hydrogen to 700 bar at ambient temp.). To validate our in silico MOF construction method, we synthesized a new isoreticular family of MOFs (she-MOF-x series) based on the she topol., which is extremely rare among MOFs. To validate our hydrogen storage predictions, we activated and measured hydrogen adsorption on she-MOF-1 and NU-1103. The latter MOF showed outstanding stability and a good combination of volumetric and gravimetric performance, presenting 43.2 g L-1 of MOF and 12.6 wt% volumetric and gravimetric deliverable capacities, resp.
- 67Moosavi, S. M.; Nandy, A.; Jablonka, K. M.; Ongari, D.; Janet, J. P.; Boyd, P. G.; Lee, Y.; Smit, B.; Kulik, H. J. Understanding the Diversity of the Metal-Organic Framework Ecosystem. Nat. Commun. 2020, 11 (1), 4068 DOI: 10.1038/s41467-020-17755-867https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhs1WrsbfE&md5=d9ba7ae4ec44a4716746a8a21b2edf0dUnderstanding the diversity of the metal-organic framework ecosystemMoosavi, Seyed Mohamad; Nandy, Aditya; Jablonka, Kevin Maik; Ongari, Daniele; Janet, Jon Paul; Boyd, Peter G.; Lee, Yongjin; Smit, Berend; Kulik, Heather J.Nature Communications (2020), 11 (1), 4068CODEN: NCAOBW; ISSN:2041-1723. (Nature Research)Abstr.: Millions of distinct metal-org. frameworks (MOFs) can be made by combining metal nodes and org. linkers. At present, over 90,000 MOFs have been synthesized and over 500,000 predicted. This raises the question whether a new exptl. or predicted structure adds new information. For MOF chemists, the chem. design space is a combination of pore geometry, metal nodes, org. linkers, and functional groups, but at present we do not have a formalism to quantify optimal coverage of chem. design space. In this work, we develop a machine learning method to quantify similarities of MOFs to analyze their chem. diversity. This diversity anal. identifies biases in the databases, and we show that such bias can lead to incorrect conclusions. The developed formalism in this study provides a simple and practical guideline to see whether new structures will have the potential for new insights, or constitute a relatively small variation of existing structures.
- 68Wragg, D. S.; Morris, R. E.; Burton, A. W. Pure Silica Zeolite-Type Frameworks: A Structural Analysis. Chem. Mater. 2008, 20 (4), 1561– 1570, DOI: 10.1021/cm071824j68https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXntVemsg%253D%253D&md5=3c89ab0b413a8335cf5e5a4552348698Pure Silica Zeolite-type Frameworks: A Structural AnalysisWragg, David S.; Morris, Russell E.; Burton, Allen W.Chemistry of Materials (2008), 20 (4), 1561-1570CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Since the last major study of silicate crystal structures, many new pure SiO2 zeolite-type frameworks were discovered. These materials have many interesting properties that are dependent on their structure. The authors have brought together and analyzed the structures in 35 well-defined frameworks to see how they differ from one another depending on the synthetic route, template, calcination, and compn., and how they differ from the dense silicate phases previously examd. The grand mean values of the Si-O bond distance and the O-Si-O angle are 1.594 A and 109.5°, resp. The variation and flexibility of the Si-O-Si bond from 133.6 to 180° is discussed, as is the role of fluoride in influencing the O-Si-O bond angles in phases prepd. using HF and ammonium fluoride as mineralizers.
- 69Noh, K.; Lee, J.; Kim, J. Compositions and Structures of Zeolitic Imidazolate Frameworks. Isr. J. Chem. 2018, 58 (9–10), 1075– 1088, DOI: 10.1002/ijch.20180010769https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhvFKjtrvO&md5=4ed9488602f6da4d26bbbb60b8341804Compositions and Structures of Zeolitic Imidazolate FrameworksNoh, Kyungkyou; Lee, Jisu; Kim, JaheonIsrael Journal of Chemistry (2018), 58 (9-10), 1075-1088CODEN: ISJCAT; ISSN:0021-2148. (Wiley-VCH Verlag GmbH & Co. KGaA)A review. Zeolitic imidazolate frameworks (ZIFs), which are composed of point metal centers and imidazolate linkers, can adopt numerous three-dimensional structures. Their unique structures and porosity properties make ZIFs promising materials esp. for gas sepn. applications. Recently their unusual phase transition properties are getting research attention rapidly. Indeed, all the properties of ZIFs are dependent on their structures. Although some empirical rules are known for discovering new ZIFs, still scientific intuition and trials are necessary to find proper reaction conditions. Also, practical information should be extd. from the accumulate achievements and in turn, applied to further exploration. In this regard, this article analyses the structures, compns., and porosity of known ZIFs, where the relationship between imidazolates and topologies is described in detail.
- 70Lee, S.; Nam, D.; Yang, D. C.; Choe, W. Unveiling Hidden Zeolitic Imidazolate Frameworks Guided by Intuition-Based Geometrical Factors. Small 2023, 19 (15), 2300036 DOI: 10.1002/smll.202300036There is no corresponding record for this reference.
- 71O’Keeffe, M. Tetrahedral Frameworks TX2 with T–X–T Angle = 180°. Mater. Res. Bull. 2006, 41 (5), 911– 915, DOI: 10.1016/j.materresbull.2005.12.013There is no corresponding record for this reference.
- 72Hohenberg, P.; Kohn, W. Inhomogeneous Electron Gas. Phys. Rev. 1964, 136 (3B), B864– B871, DOI: 10.1103/PhysRev.136.B864There is no corresponding record for this reference.
- 73Kamakoti, P.; Barckholtz, T. A. Role of Germanium in the Formation of Double Four Rings in Zeolites. J. Phys. Chem. C 2007, 111 (9), 3575– 3583, DOI: 10.1021/jp065092e73https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXitF2itLo%253D&md5=4cf1823da5d57f0168195c15e4f7a0b7Role of Germanium in the Formation of Double Four Rings in ZeolitesKamakoti, Preeti; Barckholtz, Timothy A.Journal of Physical Chemistry C (2007), 111 (9), 3575-3583CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)In recent years, novel zeolites contg. double four rings (D4Rs) were synthesized by introducing Ge into the synthesis mixt. While the structure-directing effects of Ge toward D4R contg. structures are known, little is known about the underlying chem. Plane wave d. functional theory calcns. were used to characterize and rationalize the site preferences, energies, and structural changes occurring when Ge is gradually substituted into the BEC framework up to 25% loadings. The calcns. show that the site preference and energies are strongly dictated by the intrinsic flexibility of a given T-O-T linkage (T = Si or Ge), coupled with its ability to relax to geometries preferred by Ge. Calcns. on small mol. fragments were used to explore the geometric variations in Ge-substituted zeolites and provide further insight into the role of Ge in stabilizing D4R units.
- 74Sastre, G.; Corma, A. Predicting Structural Feasibility of Silica and Germania Zeolites. J. Phys. Chem. C 2010, 114 (3), 1667– 1673, DOI: 10.1021/jp909348s74https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXhtFKjsA%253D%253D&md5=c366d86248e7ab7e09af0be1494e806fPredicting Structural Feasibility of Silica and Germania ZeolitesSastre, German; Corma, AvelinoJournal of Physical Chemistry C (2010), 114 (3), 1667-1673CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)High throughput exptl. techniques for zeolite synthesis, combined with the introduction of germanium in the synthesis gel, have allowed an increase in the no. of new zeolites, esp. of those contg. large and extralarge pores. Zeolite phases contg. Si/Ge as tetrahedral atoms stabilize certain unique topologies. One particular feature of Ge-contg. zeolites is the stabilization of small TOT (T = Si, Ge) angles compared to their silica counterparts. This study employs computational chem. techniques to calc. and rationalize the relative stability of zeolite phases as silicates and germanates. Atomistic force fields are used to simulate the structural properties of exptl. synthesized Si/Ge-contg. zeolites, and an ab initio Hartree-Fock methodol. is used to est. the energetics of TOT angles. It is shown that each particular topol. is only compatible with certain ranges of TOT angles, and, depending on the chem. compn., this induces stability or strain. A calcn. of the energetic penalty assocd. with TOT angles for the different chem. compns. at each topol. allows an est. of their feasibility. The results are in agreement with expts. and allow one to make predictions about feasibility of new SiO2 or GeO2 zeolite structures.
- 75Sartbaeva, A.; Wells, S. A.; Treacy, M. M. J.; Thorpe, M. F. The Flexibility Window in Zeolites. Nat. Mater. 2006, 5 (12), 962– 965, DOI: 10.1038/nmat178475https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28Xht1Gku7bF&md5=ab90f15fc9eecd544d6249222427d6a5The flexibility window in zeolitesSartbaeva, Asel; Wells, Stephen A.; Treacy, M. M. J.; Thorpe, M. F.Nature Materials (2006), 5 (12), 962-965CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)A mol. geometric simulation of zeolite structures was carried out to rationalize hypothetical geometric structures of zeolite cages, based on energy minimization, in order to provide criteria capable of predicting new zeolite structures. All realizable zeolite framework structures showed a flexibility window over a range of densities. This flexibility window is conjectured to be a necessary structural feature that enables zeolite synthesis, and therefore provides a valuable selection criterion when evaluating hypothetical zeolite framework structures as potential synthetic targets. This flexibility is a general feature that exptl. densities of silica zeolites lie at the low-d. edge of this window because the pores are driven to their max. vol. by Coulomb inflation (i.e., repulsion, probably between oxygen anions). This is in contrast to most solids, which have the highest d. consistent with the local chem. and geometrical constraints.
- 76Liu, X.-Y.; Yan, X.-Y.; Liu, Y.; Qu, H.; Wang, Y.; Wang, J.; Guo, Q.-Y.; Lei, H.; Li, X.-H.; Bian, F.; Cao, X.-Y.; Zhang, R.; Wang, Y.; Huang, M.; Lin, Z.; Meijer, E. W.; Aida, T.; Kong, X.; Cheng, S. Z. D. Self-Assembled Soft Alloy with Frank–Kasper Phases beyond Metals. Nat. Mater. 2024, 23 (4), 570– 576, DOI: 10.1038/s41563-023-01796-7There is no corresponding record for this reference.
- 77Sikirić, M. D.; Deza, M. Space Fullerenes: Computer Search for New Frank–Kasper Structures II. Struct. Chem. 2012, 23 (4), 1103– 1114, DOI: 10.1007/s11224-012-0005-3There is no corresponding record for this reference.
- 78Kim, K.; Schulze, M. W.; Arora, A.; Lewis, R. M.; Hillmyer, M. A.; Dorfman, K. D.; Bates, F. S. Thermal Processing of Diblock Copolymer Melts Mimics Metallurgy. Science 2017, 356 (6337), 520– 523, DOI: 10.1126/science.aam721278https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXmvVGnsL4%253D&md5=e4c0910b1cfe7651f2c414155d12e280Thermal processing of diblock copolymer melts mimics metallurgyKim, Kyungtae; Schulze, Morgan W.; Arora, Akash; Lewis, Ronald M., III; Hillmyer, Marc A.; Dorfman, Kevin D.; Bates, Frank S.Science (Washington, DC, United States) (2017), 356 (6337), 520-523CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)Small-angle x-ray scattering expts. conducted with compositionally asym. low molar mass poly(isoprene)-b-poly(lactide) diblock copolymers reveal an extraordinary thermal history dependence. The development of distinct periodic cryst. or aperiodic quasicryst. states depends on how specimens are cooled from the disordered state to temps. below the order-disorder transition temp. Whereas direct cooling leads to the formation of documented morphologies, rapidly quenched samples that are then heated from low temp. form the hexagonal C14 and cubic C15 Laves phases commonly found in metal alloys. Self-consistent mean-field theory calcns. show that these, and other assocd. Frank-Kasper phases, have nearly degenerate free energies, suggesting that processing history drives the material into long-lived metastable states defined by self-assembled particles with discrete populations of vols. and polyhedral shapes.
- 79Materials Studio v7.0; Accelrys Software Inc.: San Diego, CA 92121, USA.There is no corresponding record for this reference.
Supporting Information
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacsau.4c00285.
Materials and general procedures; detailed experimental and computational methods; characterization of FKMOFs including 1H NMR, PXRD, and SCXRD; measurements of structural information (PDF)
FKMOF-1 (CIF)
FKMOF-2 (CIF)
Models for hypothetical FKMOFs (ZIP)
CCDC 1847765 (FKMOF-1) and 1487207 (FKMOF-2) contains the supporting crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre,12 Union Road, Cambridge CB2 1EZ, U.K.; fax: + 44 1223 336033.
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