ACS Publications. Most Trusted. Most Cited. Most Read
Polynuclear Iron(II) Complexes with 2,6-Bis(pyrazol-1-yl)pyridine-anthracene Ligands Exhibiting Highly Distorted High-Spin Centers
My Activity
    Article

    Polynuclear Iron(II) Complexes with 2,6-Bis(pyrazol-1-yl)pyridine-anthracene Ligands Exhibiting Highly Distorted High-Spin Centers
    Click to copy article linkArticle link copied!

    • Ivan Šalitroš*
      Ivan Šalitroš
      Department of Inorganic Chemistry, Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava, Bratislava SK-81237, Slovakia
      Department of Inorganic Chemistry, Faculty of Science, Palacký University, 17. listopadu 12, 771 46 Olomouc, Czech Republic
      *(I.S.) E-mail: [email protected]
    • Radovan Herchel
      Radovan Herchel
      Department of Inorganic Chemistry, Faculty of Science, Palacký University, 17. listopadu 12, 771 46 Olomouc, Czech Republic
    • Olaf Fuhr
      Olaf Fuhr
      Institut für Nanotechnologie  and  Karlsruhe Nano Micro Facility (KNMF), Karlsruher Institut für Technologie, Postfach 3640, Karlsruhe 76021, Germany
      More by Olaf Fuhr
    • Rodrigo González-Prieto
      Rodrigo González-Prieto
      Departamento de Química Inorgánica, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Ciudad Universitaria, E-28040 Madrid, Spain
    • Mario Ruben*
      Mario Ruben
      Institut für Nanotechnologie, Karlsruher Institut für Technologie, Postfach 3640, Karlsruhe 76021, Germany
      Institute de Physique et Chimie de Matériaux de Strasbourg (IPCMS), CNRS-Université de Strasbourg, 23, rue du Loess, BP 43 67034 Strasbourg cedex 2, France
      *(M.R.) E-mail: [email protected]
      More by Mario Ruben
    Other Access OptionsSupporting Information (1)

    Inorganic Chemistry

    Cite this: Inorg. Chem. 2019, 58, 7, 4310–4319
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.8b03432
    Published March 12, 2019
    Copyright © 2019 American Chemical Society

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    Two bis-tridentate ligands L1 and L2 that contain 2,6-bis(pyrazol-1-yl) pyridine N-donor embraces introduced on a anthracene-acetylene backbone were used for the synthesis of a tetranuclear compound [Fe4(L1)4](CF3SO3)8·7CH3CN (1) and a hexanuclear compound [Fe6(L2)6](CF3SO3)12·18CH3NO2·9H2O (2). The polynuclear structures of both complexes were confirmed by X-ray diffraction studies, which revealed a [2 + 2] grid-like complex cation for 1 and a closed-ring hexagonal molecular architecture for the complex cation in 2. Although both compounds contain anthracene moieties arranged in a face-to-face manner, attempts at [4 + 4] photocyclization remain unsuccessful, which can be explained either by steric restraints or by inhibition of the photo-cycloaddition. Magnetic studies identified gradual and half-complete thermal spin crossover in the tetranuclear grid 1, where 50% of ferrous atoms exhibit thermal as well as photoinduced spin state switching and the remaining half of iron(II) centers are permanently blocked in their high-spin state. On the contrary, the hexanuclear compound 2 exhibits complete blocking in a high-spin state. Analysis of the magnetic data reveals the zero-field splitting parameter |D| ≈ 6–8 cm–1 with a large rhombicity for all high-spin iron(II) atoms in 1 or 2. The electronic structures and the magnetic anisotropies were also investigated by the multireference CASSCF/NEVPT2 method, and intramolecular exchange interactions were calculated by density functional theory methods.

    Copyright © 2019 American Chemical Society

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Supporting Information

    Click to copy section linkSection link copied!

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b03432.

    • Synthesis and structural, magnetic, and computational details (PDF)

    Accession Codes

    CCDC 18622421862243 contain the supplementary 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, UK; 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.

    Cited By

    Click to copy section linkSection link copied!
    Citation Statements
    Explore this article's citation statements on scite.ai

    This article is cited by 24 publications.

    1. Izar Capel Berdiell, Evridiki Michaels, Orde Q. Munro, Malcolm A. Halcrow. A Survey of the Angular Distortion Landscape in the Coordination Geometries of High-Spin Iron(II) 2,6-Bis(pyrazolyl)pyridine Complexes. Inorganic Chemistry 2024, 63 (5) , 2732-2744. https://doi.org/10.1021/acs.inorgchem.3c04138
    2. Guanping Li, Olaf Stefanczyk, Kunal Kumar, Koji Nakabayashi, Shin-ichi Ohkoshi. Nonlinear Optical and Magnetic Properties of FeII-SCN-HgII Isomers: Centrosymmetric Layers and Chiral Networks. Inorganic Chemistry 2023, 62 (7) , 3278-3287. https://doi.org/10.1021/acs.inorgchem.2c04382
    3. Aparup Paul, Ennio Zangrando, Apu Patra, Manas Kumar Mahish, Dama Saren, Hyuma Masu, Subal Chandra Manna. Tetranuclear and 1D Polymeric Cd(II) Complexes with a Tetrapyridyl Imidazolidine Ligand: Synthesis, Structure, and Fluorescence Sensing Activity. Crystal Growth & Design 2020, 20 (5) , 2904-2913. https://doi.org/10.1021/acs.cgd.9b01192
    4. Alina Dragulescu-Andrasi, Oleksandr Hietsoi, Ökten Üngör, Paul W. Dunk, Victoria Stubbs, Alejandra Arroyave, Kirill Kovnir, Michael Shatruk. Dicyanometalates as Building Blocks for Multinuclear Iron(II) Spin-Crossover Complexes. Inorganic Chemistry 2019, 58 (18) , 11920-11926. https://doi.org/10.1021/acs.inorgchem.9b01121
    5. Alexandra Šagátová, Kamil Kotrle, Barbora Brachňaková, Lubomír Havlíček, Ivan Nemec, Radovan Herchel, Monika Hofbauerova, Yuriy Halahovets, Peter Šiffalovič, Erik Čižmár, Ondřej F. Fellner, Ivan Šalitroš. Above room temperature spin crossover in mononuclear iron( ii ) complexes featuring pyridyl-benzimidazole bidentate ligands adorned with aliphatic chains. Dalton Transactions 2024, 53 (33) , 14037-14045. https://doi.org/10.1039/D4DT01338G
    6. Jun-Li Wang, Hang-Yue Zhou, Liang Zhao, Yin-Shan Meng, Tao Liu. Reversible light-induced spin state switching in a dinuclear Fe( ii ) spin crossover complex. Dalton Transactions 2024, 53 (18) , 7669-7676. https://doi.org/10.1039/D3DT02691D
    7. Rais Ahmad Khan, Amal AlFawaz, Afnan Abdullah Alhamed, Nouf Abdulrahman AlMuryyi, Imran Hasan, Anup Paul, Saad G. Alshammari, Ahmed Rashed A. Abdulwahab, Hadi D. Arman, Ali Alsalme. Cadmium (II) metal–organic architecture based on versatile multi‐N‐donor “3,5‐diaminotriazole” and dicarboxylate spacer: Synthesis, crystal structure, and its photocatalytic degradation of organic dye. Applied Organometallic Chemistry 2024, 38 (5) https://doi.org/10.1002/aoc.7426
    8. Jorge Navarro Giraldo, Jakub Hrubý, Šárka Vavrečková, Ondřej F. Fellner, Lubomír Havlíček, DaVonne Henry, Shehan de Silva, Radovan Herchel, Miroslav Bartoš, Ivan Šalitroš, Vinicius T. Santana, Paola Barbara, Ivan Nemec, Petr Neugebauer. Tetracoordinate Co( ii ) complexes with semi-coordination as stable single-ion magnets for deposition on graphene. Physical Chemistry Chemical Physics 2023, 25 (43) , 29516-29530. https://doi.org/10.1039/D3CP01426F
    9. Rafal Kulmaczewski, Malcolm A. Halcrow. Iron( ii ) complexes of 2,6-bis(imidazo[1,2- a ]pyridin-2-yl)pyridine and related ligands with annelated distal heterocyclic donors. Dalton Transactions 2023, 52 (41) , 14928-14940. https://doi.org/10.1039/D3DT02747C
    10. Guo-Hui Zhao, Shi-Hui Zhang, Cheng Yi, Tao Liu, Yin-Shan Meng. Construction of spin crossover-fluorescence bifunctional iron( ii ) complexes with modified bis(pyrazole)pyridine ligands. New Journal of Chemistry 2023, 47 (23) , 10967-10972. https://doi.org/10.1039/D3NJ01431B
    11. Lorenzo Marchi, Simone Fantuzzi, Andrea Cingolani, Alessandro Messori, Rita Mazzoni, Stefano Zacchini, Marina Cocchi, Luca Rigamonti. A proficient multivariate approach for iron( ii ) spin crossover behaviour modelling in the solid state. Dalton Transactions 2023, 52 (22) , 7684-7694. https://doi.org/10.1039/D3DT00847A
    12. Cheng Yi, Shi-Hui Zhang, Liang Zhao, Nian-Tao Yao, Guo-Hui Zhao, Yin-Shan Meng, Tao Liu. Constructing spin crossover-fluorescence bifunctional iron( ii ) complexes based on tetraphenyl ethylene-decorated AIEgens. Dalton Transactions 2023, 52 (16) , 5169-5175. https://doi.org/10.1039/D2DT04130H
    13. Rafal Kulmaczewski, Isaac T. Armstrong, Pip Catchpole, Emily S. J. Ratcliffe, Hari Babu Vasili, Stuart L. Warriner, Oscar Cespedes, Malcolm A. Halcrow. Di‐Iron(II) [2+2] Helicates of Bis‐(Dipyrazolylpyridine) Ligands: The Influence of the Ligand Linker Group on Spin State Properties. Chemistry – A European Journal 2023, 29 (9) https://doi.org/10.1002/chem.202202578
    14. Jose de Jesus Velazquez-Garcia, Krishnayan Basuroy, Darina Storozhuk, Joanne Wong, Serhiy Demeshko, Franc Meyer, Robert Henning, Simone Techert. Short- vs . long-range elastic distortion: structural dynamics of a [2 × 2] tetrairon( ii ) spin crossover grid complex observed by time-resolved X-Ray crystallography. Dalton Transactions 2022, 51 (46) , 17558-17566. https://doi.org/10.1039/D2DT02638D
    15. Jia-Hui Liu, Xiao-Qing Guo, Zi-Cheng Wang, Li-Xuan Cai, Li-Peng Zhou, Chong-Bin Tian, Qing-Fu Sun. Cation modulated spin state and near room temperature transition within a family of compounds containing the same [FeL 2 ] 2− center. Dalton Transactions 2022, 51 (10) , 3894-3901. https://doi.org/10.1039/D1DT04254H
    16. Cheng Liu. Solvent-induced synthesis and crystal structures of copper(II) complexes derived from 4-chloro-2-[(2-hydroxymethylphenylimino)methyl]phenol with antibacterial activity. Journal of Coordination Chemistry 2021, 74 (17-20) , 2972-2983. https://doi.org/10.1080/00958972.2021.2002851
    17. Takuya Shiga, Minami Tachibana, Hajime Sagayama, Reiji Kumai, Graham N. Newton, Hiroki Oshio, Masayuki Nihei. A ring of grids: a giant spin-crossover cluster. Chemical Communications 2021, 57 (79) , 10162-10165. https://doi.org/10.1039/D1CC04346C
    18. Matthias Hardy, Jacopo Tessarolo, Julian J. Holstein, Niklas Struch, Norbert Wagner, Ralf Weisbarth, Marianne Engeser, Johannes Beck, Shinnosuke Horiuchi, Guido H. Clever, Arne Lützen. Eine Familie von Heterobimetallischen Würfeln zeigt Spin‐Crossover‐Verhalten nahe Raumtemperatur. Angewandte Chemie 2021, 133 (41) , 22736-22743. https://doi.org/10.1002/ange.202108792
    19. Matthias Hardy, Jacopo Tessarolo, Julian J. Holstein, Niklas Struch, Norbert Wagner, Ralf Weisbarth, Marianne Engeser, Johannes Beck, Shinnosuke Horiuchi, Guido H. Clever, Arne Lützen. A Family of Heterobimetallic Cubes Shows Spin‐Crossover Behaviour Near Room Temperature. Angewandte Chemie International Edition 2021, 60 (41) , 22562-22569. https://doi.org/10.1002/anie.202108792
    20. Iurii Galadzhun, Rafal Kulmaczewski, Oscar Cespedes, Malcolm A. Halcrow. Iron/2,6‐Di(pyrazol‐1‐yl)pyridine Complexes with a Discotic Pattern of Alkyl or Alkynyl Substituents. European Journal of Inorganic Chemistry 2021, 2021 (29) , 2999-3007. https://doi.org/10.1002/ejic.202100435
    21. Izar Capel Berdiell, Victor García-López, Mark J. Howard, Miguel Clemente-León, Malcolm A. Halcrow. The effect of tether groups on the spin states of iron( ii )/bis[2,6-di(pyrazol-1-yl)pyridine] complexes. Dalton Transactions 2021, 50 (21) , 7417-7426. https://doi.org/10.1039/D1DT01076J
    22. Rafal Kulmaczewski, Faith Bamiduro, Namrah Shahid, Oscar Cespedes, Malcolm A. Halcrow. Structural Transformations and Spin‐Crossover in [Fe L 2 ] 2+ Salts ( L= 4‐{ tert ‐Butylsulfanyl}‐2,6‐di{pyrazol‐1‐yl}pyridine): The Influence of Bulky Ligand Substituents. Chemistry – A European Journal 2021, 27 (6) , 2082-2092. https://doi.org/10.1002/chem.202004072
    23. Jinwei Chen, Yu Li, Jinzhong Gu, Marina V. Kirillova, Alexander M. Kirillov. Introducing a flexible tetracarboxylic acid linker into functional coordination polymers: synthesis, structural traits, and photocatalytic dye degradation. New Journal of Chemistry 2020, 44 (37) , 16082-16091. https://doi.org/10.1039/D0NJ03628E
    24. O. A. Turanova, M. Yu. Volkov, E. N. Frolova, L. Bazan, G. G. Garifzianova, L. G. Gafiyatullin, I. V. Ovchinnikov, A. N. Turanov. Effect of the chemical structure of an equatorial ligand on the spin crossover properties of the Fe(III) complex with 4-styrylpyridine axial ligands. The Journal of Chemical Physics 2020, 152 (1) https://doi.org/10.1063/1.5124369

    Inorganic Chemistry

    Cite this: Inorg. Chem. 2019, 58, 7, 4310–4319
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.8b03432
    Published March 12, 2019
    Copyright © 2019 American Chemical Society

    Article Views

    1399

    Altmetric

    -

    Citations

    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.