Synthesis and Redox Activity of “Clicked” Triazolylbiferrocenyl Polymers, Network Encapsulation of Gold and Silver Nanoparticles and Anion Sensing
- Amalia Rapakousiou ,
- Christophe Deraedt ,
- Joseba Irigoyen ,
- Yanlan Wang ,
- Noël Pinaud ,
- Lionel Salmon ,
- Jaime Ruiz ,
- Sergio Moya , and
- Didier Astruc
Abstract

The design of redox-robust polymers is called for in view of interactions with nanoparticles and surfaces toward applications in nanonetwork design, sensing, and catalysis. Redox-robust triazolylbiferrocenyl (trzBiFc) polymers have been synthesized with the organometallic group in the side chain by ring-opening metathesis polymerization using Grubbs-III catalyst or radical polymerization and with the organometallic group in the main chain by Cu(I) azide alkyne cycloaddition (CuAAC) catalyzed by [Cu(I)(hexabenzyltren)]Br. Oxidation of the trzBiFc polymers with ferricenium hexafluorophosphate yields the stable 35-electron class-II mixed-valent biferrocenium polymer. Oxidation of these polymers with AuIII or AgI gives nanosnake-shaped networks (observed by transmission electron microscopy and atomic force microscopy) of this mixed-valent FeIIFeIII polymer with encapsulated metal nanoparticles (NPs) when the organoiron group is located on the side chain. The factors that are suggested to be synergistically responsible for the NP stabilization and network formation are the polymer bulk, the trz coordination, the nearby cationic charge of trzBiFc, and the inter-BiFc distance. For instance, reduction of such an oxidized trzBiFc-AuNP polymer to the neutral trzBiFc-AuNP polymer with NaBH4 destroys the network, and the product flocculates. The polymers easily provide modified electrodes that sense, via the oxidized FeIIFeIII and FeIIIFeIII polymer states, respectively, ATP2– via the outer ferrocenyl units of the polymer and PdII via the inner Fc units; this recognition works well in dichloromethane, but also to a lesser extent in water with NaCl as the electrolyte.
Synopsis
Polymers containing triazolylbiferrocenyl groups in the side chain or the main chain are synthesized by ring-opening metathesis polymerization, radical or click CuAAC polycondensation and oxidized by [FeCp2][PF6], H[AuCl4], or Ag[BF4] to stable class-II mixed-valent biferrocenium salts. Various Au and Ag nanoparticle networks stabilized by triazolylbiferrocenium salts and modified electrodes are obtained, and ATP2− and PdII are recognized both in dichloromethane and in water.
Introduction
Results and Discussion
Synthesis and Characterization of triazolylBiFc Polymers 9, 10, 14, 18, and 19
Synthesis of Ethynylbiferrocene 3
Scheme 1

Synthesis of the trzBiFc-Functionalized Norbornene Monomer 7
Scheme 2

Ring-Opening-Metathesis Polymerization of the Norbornene Functionalized with a trzBiFc Group
Figure 1

Figure 1. (a) Third generation Ru metathesis catalyst, Grubbs III (8) (b) CuACC catalyst copper [CuItren(CH2Ph)6][Br] (13).
Scheme 3

Synthesis of the trzBiFc Polystyrene 14
Scheme 4

Synthesis of Triazolyl-biferrocenyl-PEG Copolymers 18 and 19 (17c)
Scheme 5

| compound | E1/2 (V)b | ΔE (mV)b | ic/iab | E1/2 (V)c | ΔE (mV)c | ic/iac |
|---|---|---|---|---|---|---|
| 3 | 0.48 | 59 | 1.0 | 0.93 | 56 | 1 |
| 7 | 0.43 | 50 | 1.1 | 0.79 | 40 | 0.8 |
| 9 | 0.42 | 15 | 1.1 | 0.76 | 20 | 1.4 |
| 10 | 0.42 | 30 | 1.8 | 0.74 | 20 | 1.3 |
| 14 | 0.41 | 10 | 1.7 | 0.72 | 15 | 1.5 |
| 17 | 0.58 | 60 | 1.1 | 0.93 | 55 | 1.0 |
| 18 | 0.44 | 55 | 1.4 | 0.79 | 40 | 1.5 |
| 19 | 0.42 | 35 | 1.3 | 0.80 | 45 | 1.0 |
Supporting electrolyte: [n-Bu4N][PF6] 0.1 M; solvent: dry CH2Cl2; working and counter electrodes: Pt; reference electrode: Ag; internal reference: FeCp*2; scan rate: 0.200 V.s–1.
Data obtained for the first wave (FeII/III).
Data obtained for the second wave (FeII/III).
Figure 2

Figure 2. CVs of (a) monomer 7, (b) polymer 9, and (c) progressive adsorption of polymer 9 onto a Pt electrode upon 20 scans around the BiFc potentials. Solvent: DCM; reference electrode: Ag; working and counter electrodes: Pt; scan rate: 0.2 V/s; supporting electrolyte: 0.1 M [n-Bu4N][PF6]. The wave at 0.0 V belongs to the internal reference FeCp*2.
Molecular Weights of Polymers 9, 10, 14, 18, and 19
| compound | conversion (%) | nta/npc | ned | nmf |
|---|---|---|---|---|
| Mono 7 | 1 | |||
| Poly 9 | 98 | 30/33 ± 4 | 32 ± 3 | 33 ± 4 |
| Poly 10 | 99 | 60/55 ± 7 | 66 ± 6 | 53 ± 7 |
| Poly 14 | 97 | 31b/– | 36 ± 4 | 29 ± 3 |
| Poly 18 | 78 | 151 ± 23e | g | |
| Poly 19 | 58 | 62 ± 12e | g |
Theoretical number of branches corresponding to [M]/[C] molar ratio.
Obtained from the SEC analysis of the organic precursor 12 (using polystyrene as standard).
Values obtained by 1H NMR end-group analysis in CD2Cl2, at 25 °C.
Number of electrons obtained by CV from eq 2.
Molecular weight of polymers 18 and 19 were calculated by eq 1 upon using the diffusion coefficients obtained from DOSY NMR analysis.
Number of metallocene units obtained by UV–vis. spectroscopy using equation: nm = ε/εo.
The equation nm= ε/εo is not adequate for polymers 18 and 19 because of the existence of the PEG units.
(1)
(2)Consequently comparison with the internal reference FeCp*2 provides a good estimation of the number of electrons np involved in the FeII/III redox process as a function of the monomer and polymer intensities (i), concentrations (c), and molecular weights (M). Measurement of the respective intensities for the reference FeCp*2 and the first anodic wave (see Supporting Information for the CVs with FeCp*2 as the reference) led to the data of ne for the polymers 9, 10, 14, 18, and 19. The ne values of polymers 9, 10, and 14 are slightly superior to the theoretical number of polymeric units, probably due to their slight adsorption on the Pt electrode starting even from the first scan around the BiFc potentials. For copolymers 18 and 19, the molecular weight was calculated only by this electrochemical method by both eqs 1 and 2 by using the diffusion coefficients of the monometallic reference FeCp*2 and polymers 18 and 19.Reaction of Polymers with AuIII: Formation of Mixed-Valent Polymers and Stabilization of Encapsulated Gold Nanoparticles by Snake-Shaped Nanonetworks
(3)Scheme 6

Scheme aPhotograph: isolated vermicular from the TEM analysis of AuNSs-14b.
Figure 3

Figure 3. (a) TEM analysis of mixed-valent biferrocenium polymer-stabilized AuNSs-14b at 0.5 μm; (b) size distribution of the AuNPs.
Figure 4

Figure 4. (a) AFM topography image (2 μm scale) of 10, (b) AFM topography image (270 nm scale) of AuNSs-10b, (c) AFM adhesion image (2 μm scale) of AuNSs-10b, and (d) AFM adhesion image (270 nm scale) of AuNSs-10b where three different regions A, B, and C are represented corresponding to three different force curves (Supporting Information).
Figure 5

Figure 5. (a) TEM of AuNPs-14c and (b) UV–vis spectrum of 14c (blue line). The violet line corresponds to the UV–vis spectrum after 5 min, and the red line is recorded after shaking of the sample. The photograph shows the flocculated AuNPs and their redissolution by shaking.
Figure 6

Figure 6. FT-IR (KBr) of (a) mixed-valent biferrocenium-stabilized AuNSs-14b, 844 cm–1 (νFc+) and 824 cm–1 (νFc), (b) polymer 14, 815 cm–1 (νFc).
Figure 7

Figure 7. (a) TEM analysis of AuNNs-18b at 200 nm, (b) UV–vis spectrum of AuNNs-18b peaking at 534 nm (plasmon band).
Scheme 7

Figure 8

Figure 8. TEM analysis of 20b at 100 nm.
Figure 9

Figure 9. (a) TEM analysis of AgNSs-21b, (b) UV–vis spectrum of AgNSs-21b showing the plasmon band of AgNPs at λ = 434 nm and the biferrocenium band at λ = 630 nm.
Modified Electrodes and Redox Recognition
Figure 10

Figure 10. (a) Modified Pt electrode of polymer 14 at various scan rates in a DCM solution containing only 0.1 M [n-Bu4N][PF6] as the supporting electrolyte; (b) intensity as a function of scan rate; linearity shows the expected behavior of an adsorbed polymer.
| compound | ΔEfwhma (mV) | Γ (mol cm–2)b | ndc |
|---|---|---|---|
| Poly 9 | 75 | 2.1 × 10–10 | 3 |
| Poly 10 | 72 | 2.9 × 10–10 | 4 |
| Poly 14 | 80 | 3.1 × 10–10 | 14 |
| Poly 18 | 115 | 10.4 × 10–10 | 1 |
Values of the full width at half-maximum.
Surface coverage of the electroactive BiFc sites of the polymers.
Number of days for which the modified electrodes show no loss of electroactivity.
Figure 11

Figure 11. Voltammetric response of a platinum electrode modified with polymer 14, measured in H2O/0.1 M NaCl; scan rate: 50 mV s–1.
Redox Sensing Using Pt Electrodes Modified with Polymer 14 in Organic Media
Figure 12

Figure 12. Recognition of ATP2– with a Pt modified electrode with polymer 14. (a) Modified electrode alone; (b) and (c) in the course of titration (the second wave is not represented as scanning until more positive potentials upon addition of ATP anions provokes instability of the electrode); (d) with an excess of [n-Bu4N]2[ATP]. Solvent: DCM; reference electrode: Ag; working and counter electrodes: Pt ; scan rate: 0.3 V/s ; supporting electrolyte: 0.1 M [nBu4N][PF6].
Redox Sensing Using Pt Electrodes Modified with Polymer 14 in Aqueous Media
Concluding Remarks
Experimental Section
General Data
Compound 5
Compound 7
Polymer 9
Polymer 10
Polymer 14
Polymer 18
Polymer 19
AuNSs-9b
AuNSs-10b
AuNSs-14b
AuNPs-14c
AuNNs-18b
AuNPs-20b
AgNSs-21b
CV Measurements
Supporting Information
Spectroscopic data for all the complexes and NMR, IR, near-IR, UV–vis. spectra and CVs. This material is available free of charge via the Internet at http://pubs.acs.org.
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.
Acknowledgment
Helpful assistance and discussion with Jean-Michel Lanier (NMR) and Claire Mouche (MALDI-TOF MS) from the CESAMO and Dr. Roberto Ciganda (Université de Bordeaux), and financial support from the Université de Bordeaux, the Centre National de la Recherche Scientifique (CNRS), the Agence Nationale pour la Recherche (ANR) and L’Oréal are gratefully acknowledged.
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This effect have allowed us to develop efficient biosensors capable of measuring NADH from +0.3 V (vs. SCE) providing a total protection vs. the poisoning of the electrodes. The polymer/PtNPs/Pt electrodes tolerate wide linear concn. ranges for NADH to 2.5 mM (R = 0.9979) and 2.1 mM (R = 0.99849), with detection limits of 4.78 μM and 6.18 μM and sensitivities of 68.24 and 40.21 μA mM-1 cm-2 for the PDAMS/PtNPs/Pt and PMDUS/PtNPs/Pt resp. In the light of the good results obtained, novel amperometric alc. biosensors were also successfully prepd. with alc. dehydrogenase (ADH). These devices showed more affinity for methanol than for ethanol, with a wide linear range to 30 mM and sensitivities of 0.957 and 0.756 μA mM-1 cm-2 for the ADH/PDAMS/PtNPs/Pt and ADH/PMDUS/PtNPs/Pt resp. The oxidn. potential of the NADH enzymically produced was neg. shifted to +0.25 V. - 8(a) Nguyen, P.; Gomez-Elipe, P.; Manners, I. Chem. Rev. 1999, 99, 1515– 1548(b) Abd-El-Aziz, A. S.; Bernardin, S. Coord. Chem. Rev. 2000, 203, 219– 267Google ScholarThere is no corresponding record for this reference.(c) Abd-El-Aziz, A. S.; Todd, E. K. Coord. Chem. Rev. 2003, 246, 3– 52Google ScholarThere is no corresponding record for this reference.(d) Macromolecules Containing Metal and Metal-Like Elements, Organoiron Polymers, Vol 2, Eds: Abd-El-Aziz, A. S.; Carraher, Jr., C. E.; Pittman, Jr., C. U.; Sheats, J. E.; Zeldin, M.; Wiley-Interscience: Hoboken: NJ, 2003.Google ScholarThere is no corresponding record for this reference.(e) Abd-El-Aziz, A. S.; Manners, I. J. Inorg. Organomet. Polym. 2005, 15, 157– 195[Crossref], [CAS], Google Scholar8ehttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXkvFCiu7s%253D&md5=26c6f693678629b6e908c6c0883fa363Neutral and cationic macromolecules based on iron sandwich complexesAbd-El-Aziz, Alaa S.; Manners, IanJournal of Inorganic and Organometallic Polymers and Materials (2005), 15 (1), 157-195CODEN: JIOPAY; ISSN:1574-1443. (Springer)A review on the synthesis, properties, and characterization of macromols. based on ferrocene or arene cyclopentadienyliron cations is presented. Ferrocene-based polymers in which the ferrocene moieties are in or pendent to the backbone are described, as well as, the use of arene cyclopentadienyliron complexes in the design of polymeric materials. The design of star-shaped macromols. and dendrimer materials that contain ferrocene and/or arene cyclopentadienyliron units are discussed as well.(f) Frontiers in Transition-Metal Containing Polymers, A. S. Abd-El-Aziz; Manners, I., Eds.; Wiley: New York, 2007.(g) Martinez, F. J.; Gonzalez, B.; Alonso, B.; Losada, J.; Garcia-Armada, M. P.; Casado, C. M. J. Inorg. Organomet. Polym. Mater. 2008, 18, 51– 58[Crossref], [CAS], Google Scholar8ghttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXptlensw%253D%253D&md5=ff5d83c4a602e62b3ec6808e20c29473Synthesis and redox properties of an electropolymerizable amido ferrocenyl pyrrole-functionalized dendrimerMartinez, Francisco J.; Gonzalez, Blanca; Alonso, Beatriz; Losada, Jose; Garcia-Armada, M. Pilar; Casado, Carmen M.Journal of Inorganic and Organometallic Polymers and Materials (2008), 18 (1), 51-58CODEN: JIOPAY; ISSN:1574-1443. (Springer)A novel ferrocenyl dendrimer functionalized with electrochem. polymerizable pyrrole substituents, with diaminobutane-based tetramido core, (DAB-dend)[(OC-η5-C5H4)Fe{η5-C5H4CONH(CH2)3NC4H4}]4 [1; H4DAB-dend = N,N,N',N'-tetrakis(3-aminopropyl)-1,4-butanediamine, NC4H4 = 1-pyrrolyl], was prepd. and characterized. A secondary reaction product, the dipyrrole deriv. [Fe{η5-C5H4CONH(CH2)3NC4H4}2] (2) also was isolated and used as a model to facilitate the characterization of 1. The mol. structure of 2 was detd. by single crystal x-ray diffraction studies. Glassy carbon electrodes have been successfully modified by electropolymn. of the pyrrole-functionalized derivs. 1 and 2, in dichloromethane/acetonitrile solns., resulting in visually detectable electroactive ferrocenyl polymer films persistently attached to the electrode surfaces. Osteryoung square wave voltammetry expts. (OSWV) showed that films of the electropolymd. dendrimer 1 (poly-1) senses H2PO4- in aq. soln. using Li[B(C6F5)4] as supporting electrolyte.
- 9(a) Manners, I. Science 2001, 294, 1664– 1666Google ScholarThere is no corresponding record for this reference.(b) Whittel, G. R.; Manners, I. Adv. Mater. 2007, 19, 3439– 3468Google ScholarThere is no corresponding record for this reference.(c) Hudson, Z.; Boot, C. E.; Robinson, M. E.; Rupar, P. A.; Winnink, M. A.; Manners, I. Nat. Chem. 2014, 6, 893– 898[Crossref], [PubMed], [CAS], Google Scholar9chttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhsFKms7rN&md5=d1c116fb9a6fb3dc89c228090cd899feTailored hierarchical micelle architectures using living crystallization-driven self-assembly in two dimensionsHudson, Zachary M.; Boott, Charlotte E.; Robinson, Matthew E.; Rupar, Paul A.; Winnik, Mitchell A.; Manners, IanNature Chemistry (2014), 6 (10), 893-898CODEN: NCAHBB; ISSN:1755-4330. (Nature Publishing Group)Recent advances in the self-assembly of block copolymers have enabled the precise fabrication of hierarchical nanostructures using low-cost soln.-phase protocols. However, the prepn. of well-defined and complex planar nanostructures in which the size is controlled in two dimensions (2D) has remained a challenge. Using a series of platelet-forming block copolymers, we have demonstrated through quant. expts. that the living crystn.-driven self-assembly (CDSA) approach can be extended to growth in 2D. We used 2D CDSA to prep. uniform lenticular platelet micelles of controlled size and to construct precisely concentric lenticular micelles composed of spatially distinct functional regions, as well as complex structures analogous to nanoscale single- and double-headed arrows and spears. These methods represent a route to hierarchical nanostructures that can be tailored in 2D, with potential applications as diverse as liq. crystals, diagnostic technol. and composite reinforcement.
- 10(a) Abakumova, L. G.; Abakumov, G. A.; Razuvaev, G. A. Dokl. Akad. Nauk SSSR 1975, 220, 1317– 1320Google ScholarThere is no corresponding record for this reference.(b) Huang, W. H.; Jwo, J. J. J. Chin, Chem. Soc. 1991, 38, 343– 350[CAS], Google Scholar10bhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK3MXlvVems7c%253D&md5=a9be599d17b047b946a48aced0e66a92Kinetics of the decomposition of ferrocenium ion and its derivativesHuang, Wen Hong; Jwo, Jing JerJournal of the Chinese Chemical Society (Taipei, Taiwan) (1991), 38 (4), 343-50CODEN: JCCTAC; ISSN:0009-4536.The first-order kinetics of the decompn. of ferrocenium ion (Fc+) and its substituted derivs. were studied in aq. sulfuric acid and in the presence of excess Ce(IV) ion. The obsd. first-order rate const. (kobs) is expressed as kobs = kd for the acyl-substituted ferrocenium ions and kobs = kd + kox[Ce(IV)0 for the unsubstituted and alkyl-substituted ferrocenium ions. Electron-donating alkyl substituents stabilize the ferrocenium ion whereas electron-withdrawing acyl substituents make it less stable. The order of relative stability toward decompn. is 1,1'-dimethyl Fc+ ≥ Bu Fc+ > 1,1-dimethylpropyl Fc+ > Fc+ >> formyl Fc+ > acetyl Fc+ >> benzoyl Fc+. A mechanism to interpret the kinetics is also given.(c) Zotti, G.; Schiavon, G.; Zecchin, S.; Berlin, A.; Pagani, G. Langmuir 1998, 14, 1728– 1733(d) Hurvois, J.-P.; Moinet, C. J. Organomet. Chem. 2005, 690, 1829– 1839[Crossref], [CAS], Google Scholar10dhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXivVSlsr4%253D&md5=5c92e755aaece09e230d85d7b6aed739Reactivity of ferrocenium cations with molecular oxygen in polar organic solvents: decomposition, redox reactions and stabilizationHurvois, J. P.; Moinet, C.Journal of Organometallic Chemistry (2005), 690 (7), 1829-1839CODEN: JORCAI; ISSN:0022-328X. (Elsevier B.V.)The behavior of chem. or electrochem. generated ferrocenium cations was studied in some polar org. solvents (DMF, DMSO, MeCN, acetone, CH2Cl2) under mol. oxygen. Adducts between oxygen and ferrocenium species can differently evolve according to the solvent (oxidizable or not) and the absence or the presence of another reagent. A rapid decompn. of ferrocenium cations is obsd. in the absence of another substrate. In the presence of some substrates and antioxidants, the stability of ferrocenium cations towards mol. oxygen notably increases and in some cases redox reactions take place with formation of ferrocene.
- 11(a) Cowan, D. O.; Kaufman, F. J. Am. Chem. Soc. 1970, 92, 219– 220(b) Cowan, D. O.; Kaufman, F. J. Am. Chem. Soc. 1971, 93, 3889– 3893(c) Levanda, C.; Cowan, D. O.; Bechgaard, K. J. Am. Chem. Soc. 1975, 97, 1980– 1981(d) Power, M. J.; Meyer, T. J. J. Am. Chem. Soc. 1978, 100, 4393– 4398Google ScholarThere is no corresponding record for this reference.
- 12(a) Robin, M. B.; Melvin, B.; Day, P. Adv. Inorg. Chem. Radiochem. 1967, 10, 247– 403[Crossref], [CAS], Google Scholar12ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaF1cXovF2isA%253D%253D&md5=2e720e6e07f03661b3eeb0fb2be3c598Mixed valence chemistry. A survey and classificationRobin, Melvin B.; Day, PeterAdvances in Inorganic Chemistry and Radiochemistry (1967), 10 (), 247-422CODEN: AICRAH; ISSN:0065-2792.A review. The theory of mixed valence effects is discussed in terms of the wave functions and mixed valence classification, mixed valence spectra, magnetism and electron transport, and mol. geometry. The mixed valence chemistry of the transition metals, Ga, In, Tl, Sn, Pb, P, As, Sb, Bi, the lanthanides, and the actinides is discussed. 820 references.(b) Allen, G. C.; Hush, N. S. Prog. Inorg. Chem. 1967, 8, 357– 390[Crossref], [CAS], Google Scholar12bhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaF1cXhtVSjsbk%253D&md5=0b16c71190cc7a504eee0068adcdca3eIntervalence-transfer absorption. I. Qualitative evidence for intervalence-transfer absorption in inorganic systems in solution and in the solid stateAllen, Geoffrey Charles; Hush, Noel S.Progress in Inorganic Chemistry (1967), 8 (), 357-89CODEN: PIOCAR; ISSN:0079-6379.The qual. evidence for intervalence-transfer absorption in inorg. systems in soln. and in the solid-state is reviewed. Sym. homonuclear, asym. homonuclear, and heteronuclear intervalence transfer are included. 116 references.(c) Richardson, D. E.; Taube, H. Coord. Chem. Rev. 1984, 60, 107– 129[Crossref], [CAS], Google Scholar12chttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL2MXht1Gjug%253D%253D&md5=f487a2ef7ad7c2f2cf6657f419237a73Mixed-valence molecules: electronic delocalization and stabilizationRichardson, David E.; Taube, HenryCoordination Chemistry Reviews (1984), 60 (), 107-29CODEN: CCHRAM; ISSN:0010-8545.A review with 40 refs.
- 13(a) Horikoshi, T.; Itoh, M.; Kurihara, M.; Kubo, K.; Nishihara, H. J. Electroanal. Chem. 1999, 473, 113– 116[Crossref], [CAS], Google Scholar13ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK1MXls1yltbc%253D&md5=47d65dd61b59d96c0bd5eac4e70e5c8bSynthesis, redox behavior and electrodeposition of biferrocene-modified gold clustersHorikoshi, T.; Itoh, M.; Kurihara, M.; Kubo, K.; Nishihara, H.Journal of Electroanalytical Chemistry (1999), 473 (1,2), 113-116CODEN: JECHES ISSN:. (Elsevier Science S.A.)Biferrocene-modified Au clusters, comprising a 2.2 ± 0.3 nm-diam. Au core covered with 20 biferrocene-terminated thiolates and 75 octyl thiolates on av., were synthesized by a substitution reaction of octanethiol-modified clusters with biferrocene-terminated alkanethiol, (η5-C5H5)Fe(C10H8)Fe(η5-C5H4CO(CH2)7SH). The biferrocene-modified cluster undergoes 2-step oxidn. reactions in NBu4ClO4 + CH2Cl2 and the 2nd oxidn. process leads to the formation of a uniform redox-active Au cluster film on electrode. The surface plasmon absorption of the cluster film depends on the oxidn. state of the redox active species on the cluster surface.(b) Nishihara, H. Bull. Soc. Chem. Jpn. 2001, 74, 19– 29[Crossref], [CAS], Google Scholar13bhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3MXhs12hsbc%253D&md5=2a4b072908622a82a1c5cf84ad11832eRedox and optical properties of conjugated ferrocene oligomersNishihara, HiroshiBulletin of the Chemical Society of Japan (2001), 74 (1), 19-29CODEN: BCSJA8; ISSN:0009-2673. (Chemical Society of Japan)A review contg. 57 refs. is presented. Internuclear electronic interactions in conjugated ferrocene oligomers display unique redox and optical properties. I describe here recent research on the dependence of such properties on the no. of ferrocene nuclei and on the structure of conjugated spacers. The neighboring-site interaction model explains the redox properties of oligo(ferrocene-1,1'-diyl)s. The IR spectra of carbonyl complex-bound diferrocene and terferrocene enlighten the electronic structure in the mixed-valence states. Energy shifts of intervalence transfer (IT) in the mixed-valence states of oligo(ferrocene-1,1'-diyl)s resulting from changes in the oxidn. state are rationalized by taking into account the change in neighboring-site combination by photoelectron transfer, which delivers extra energy due to the strain in internuclear distance. Oligo- and poly-(ferrocene-1,1'-diyl)s oxidized partially by tetracycanoethylene (TCNE) exhibit near-IR photocond. Conjugated spacer groups between ferrocene nuclei involving metal complex moieties affect the redox properties of ferrocene dimers significantly. The azo group acts as a distinctive spacer of which conjugation ability is changeable photochem.(c) Yamada, M.; Nishihara, H. Chem. Commun. 2002, 2578– 2579Google ScholarThere is no corresponding record for this reference.(d) Yamada, M.; Nishihara, H. Eur. Phys. J. 2003, 24, 257– 260[CAS], Google Scholar13dhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXntFeht78%253D&md5=25d2c9b7657e0cccfde08756882e505cCore size effects on electrodeposition of gold nanoparticles attached with biferrocene derivativesYamada, M.; Nishihara, H.European Physical Journal D: Atomic, Molecular and Optical Physics (2003), 24 (1-3), 257-260CODEN: EPJDF6; ISSN:1434-6060. (EDP Sciences)Biferrocene-modified gold nanoparticles (Aun-BFc) comprising 1.7, 2.2 and 2.9 nm in av. core diam., d, were synthesized by a substitution reaction of octyl thiolate-covered nanoparticles with biferrocene-terminated alkanethiol, 1-(9-thiononyl-1-one)-1',1''-biferrocene (BFcS). All sizes of Aun-BFc undergo two-step oxidn. reactions in 0.1 mol dm-3 Bu4NClO4-CH2Cl2 and consecutive potential scans including the second oxidn. process lead to the formation of an adhesive redox-active gold nanoparticle film on an electrode. The thickness of the Aun-BFc film is controllable by the no. of potential scans. The scanning tunneling microscope images reveal that the Aun-BFc (d = 2.9 nm) film forms many domains of the assembled Aun-BFcs, esp. the particles are isotropically assembled in line.(e) Yamada, M.; Nishihara, H. Langmuir 2003, 19, 8050– 8056(f) Yamada, M.; Nishihara, H. ChemPhysChem 2004, 5, 555– 559Google ScholarThere is no corresponding record for this reference.(g) Yamada, M.; Tadera, T.; Kubo, K.; Nishihara, H. J. Phys. Chem. B 2003, 107, 3703– 3711(h) Muraa, M.; Nishihara, H. J. Inorg. Organomet. Polym. 2005, 15, 147– 156
- 14Nijhuis, C. A.; Dolatowska, K. A.; Ravoo, B. J.; Huskens, J.; Reinhoudt, D. N. Chem.—Eur. J. 2007, 13, 69– 80[Crossref], [PubMed], [CAS], Google Scholar14https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXitlCisA%253D%253D&md5=6d639f0b3873cbe0e2bf64fba4ed24d7Redox-controlled interaction of biferrocenyl-terminated dendrimers with β-cyclodextrin molecular printboardsNijhuis, Christian A.; Dolatowska, Karolina A.; Ravoo, Bart Jan; Huskens, Jurriaan; Reinhoudt, David N.Chemistry--A European Journal (2007), 13 (1), 69-80CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)This paper describes the synthesis and electrochem. of biferrocenyl-terminated dendrimers and their β-cyclodextrin (β-CD) inclusion complexes in aq. soln. and at surfaces. Three generations of Poly(propyleneimine) (PPI) dendrimers, decorated with 4, 8, and 16 biferrocenyl (BFc) units, resp., were synthesized. A H2O-sol. BFc deriv. forms stable inclusion complexes with β-CD. The intrinsic binding const. is Ki = 2.5 × 104M-1. The BFc dendrimers were solubilized in H2O by complexation of the end groups with β-CD, resulting in large H2O-sol. supramol. assemblies. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) showed that all the end groups are complexed to β-CD. Adsorption of the dendrimers at self-assembled monolayers (SAMs) of heptathioether-functionalized β-CD on Au (mol. print-boards) resulted in stable monolayers of the dendrimers due to the formation of multivalent host-guest interactions between the BFc end groups of the dendrimers and the immobilized β-CD mols. The no. of interacting end groups is 3, 4, and 4 for dendrimers generations 1, 2, and 3, resp. The complexation of BFc to β-CD is sensitive to the oxidn. state of the BFc unit. Oxidn. of neutral BFc-Fe2(II,II) to the cationic, mixed-valence biferrocenium BFc-Fe2(II,III)+ resulted in dissocn. of the host-guest complexes. Scan-rate-dependent CV and DPV analyses of the dendrimers-β-CD assemblies immobilized at the β-CD host surface and in soln. revealed that the dendrimers are oxidized in 3 steps. First, the surface-β-CD-bound BFc moieties are oxidized to the mixed-valence state, Fe2(II,III)+, followed by the oxidn. of the nonsurface-interacting BFc groups to the Fe2(II,III)+ state. The 3rd step involves the oxidn. of all the BFc moieties to the Fe2(III,III)2+ state.
- 15Wimbush, K. S.; Reus, W. F.; van der Wiel, W. G.; Reinhoudt, D. N.; Whitesides, G. M.; Nijhuis, C. A.; Velders, A. H. Angew. Chem., Int. Ed. 2010, 49, 10176– 10180Google ScholarThere is no corresponding record for this reference.
- 16(a) Ochi, Y.; Suzuki, M.; Imaoka, T.; Murata, M.; Nishihara, H.; Einaga, Y.; Yamamoto, K. J. Am. Chem. Soc. 2010, 132, 5061– 5069(b) Cuadrado, I.; Casado, C. M.; Alonso, B.; Moran, M.; Losada, J.; Belsky, V. J. Am. Chem. Soc. 1997, 119, 7613– 7614(c) Villena, C.; Losada, J.; Garcia-Armada, P.; Casado, C. M.; Alonso, B. Organometallics 2012, 31, 3284– 3291
- 17(a) Yamamoto, T.; Morikita, T.; Maruyama, T.; Kubota, K.; Katada, M. Macromolecules 1997, 30, 5390– 5396(b) Yan, S. G.; Hupp, J. T. J. Electroanal. Chem. 1995, 397, 119– 26Google ScholarThere is no corresponding record for this reference.(c) Deraedt, C.; Rapakousiou, A.; Wang, Y.; Salmon, L.; Bousquet, M.; Astruc, D. Angew. Chem., Int. Ed. 2014, 53, 8445– 8449Google ScholarThere is no corresponding record for this reference.
- 18(a) Wang, Y.; Rapakousiou, A.; Chastanet, G.; Salmon, L.; Ruiz, J.; Astruc, D. Organometallics 2013, 32, 6136– 6146(b) Djeda, R.; Rapakousiou, A.; Liang, L.; Guidolin, N.; Ruiz, J.; Astruc, D. Angew. Chem., Int. Ed. 2010, 49, 8152– 8156Google ScholarThere is no corresponding record for this reference.(c) Astruc, D.; Liang, L.; Rapakousiou, A.; Ruiz, J. Acc. Chem. Res. 2012, 45, 630– 640[ACS Full Text
], [CAS], Google Scholar18chttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXhsF2lsb%252FM&md5=4e92ae2e4efc86a9c29587233d53db15Click Dendrimers and Triazole-Related Aspects: Catalysts, Mechanism, Synthesis, and Functions. A Bridge between Dendritic Architectures and NanomaterialsAstruc, Didier; Liang, Liyuan; Rapakousiou, Amalia; Ruiz, JaimeAccounts of Chemical Research (2012), 45 (4), 630-640CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)A review. One of the primary recent improvements in mol. chem. is the now decade-old concept of click chem. Typically performed as copper-catalyzed azide-alkyne (CuAAC) Huisgen-type 1,3-cycloaddns., this reaction has many applications in biomedicine and materials science. The application of this chem. in dendrimer synthesis beyond the zeroth generation and in nanoparticle functionalization requires stoichiometric use of the most common click catalyst, CuSO4·5H2O with sodium ascorbate. Efforts to develop milder reaction conditions for these substrates have led to the design of polydentate nitrogen ligands. Along these lines, we have described a new, efficient, practical, and easy-to-synthesize catalytic complex, [CuI(hexabenzyltren)]Br, 1 [tren = tris(2-aminoethyl)amine], for the synthesis of relatively large dendrimers and functional gold nanoparticles (AuNPs). This efficient catalyst can be used alone in 0.1% mol amts. for nondendritic click reactions or with the sodium-ascorbate additive, which inhibits aerobic catalyst oxidn. Alternatively, catalytic quantities of the air-stable compds. hexabenzyltren and CuBr added to the click reaction medium can provide analogously satisfactory results. Based on this catalyst as a core, we have also designed and synthesized analogous CuI-centered dendritic catalysts that are much less air-sensitive than 1 and are sol. in org. solvents or in water (depending on the nature of the terminal groups). These multivalent catalysts facilitate efficient click chem. and exert pos. dendritic effects that mimic enzyme activity. We propose a monometallic CuAAC click mechanism for this process. Although the primary use of click chem. with dendrimers has been to decorate dendrimers with a large no. of mols. for medicinal or materials purposes, we are specifically interested in the formation of intradendritic [1,2,3]-triazole heterocycles that coordinate to transition-metal ions via their nitrogen atoms. We describe applications including mol. recognition of anions and cations and the stabilization of transition metal nanoparticles according to a principle pioneered by Crooks with poly(amido amine) (PAMAM) dendrimers, and in particular, the control of structural and reactivity parameters in which the intradendritic [1,2,3]-triazoles and peripheral tripodal tri(ethylene glycol) termini play key roles in the click-dendrimer mediated synthesis and stabilization of gold nanoparticles (AuNPs). By varying these parameters, we have stabilized water-sol., weakly liganded AuNPs between 1.8 and 50 nm in size and have shown large differences in behavior between AuNPs and PdNPs. Overall, the new catalyst design and the possibilities of click dendrimer chem. introduce a bridge between dendritic architectures and the world of nanomaterials for multiple applications.(d) Poppitz, E. A.; Hildebrandt, A.; Korb, N.; Lang, H. J. Organomet. Chem. 2014, 752, 133– 140[Crossref], [CAS], Google Scholar18dhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXkvFOmug%253D%253D&md5=12e0681a15b684efda0c707984d6ba03Di(biferrocenyl)ethyne and -butadiyne: synthesis, properties and electron transfer studiesPoppitz, Elisabeth Andrea; Hildebrandt, Alexander; Korb, Marcus; Lang, HeinrichJournal of Organometallic Chemistry (2014), 752 (), 133-140CODEN: JORCAI; ISSN:0022-328X. (Elsevier B.V.)Di(biferrocenyl)ethyne (3) and -butadiyne (4) have been prepd. by Negishi, Eglinton and Sonogashira C,C cross-coupling reactions using 1'-iodo-1,1''-biferrocene (1) and 1'-ethynyl-1,1''-biferrocene (2) as starting materials. Compd. 4 was structurally analyzed by single crystal x-ray diffraction studies. The individual ferrocenyl units are all coplanar and anti-parallel oriented. Electrochem. measurements showed that all four ferrocenyl units can reversibly be oxidized. The electrochem. characteristics of these mols. represent a combination of the properties of biferrocene and the appropriate ferrocenyl analogs diferrocenyl ethyne and diferrocenyl butadiyne, resp. While the dicationic oxidn. state of both compds. showed characteristics of a charge transfer within the biferrocenium units, the tricationic form allows electron transfer through the (-C≡C-)n (n = 1, 2) functionalities. The obsd. inter-valence charge transfer (IVCT) interaction of 3 and 4 in any mixed-valent oxidn. state allowed the characterization of these species as class II systems according to Robin and Day. In situ IR spectroscopy of 3 and 4 showed that within 3n+ and 4n+ (n = 0, 2, 4) no νCC band is present, while 3+ and 33+ showed two νCC stretching vibrations due to Fermi resonance. Compd. 43+ exhibits only one sharp νCC frequency.(e) Rapakousiou, A.; Djeda, R.; Grillaud, M.; Li, N.; Ruiz, J.; Astruc, D. Organometallics 2014, DOI: 10.1021/om501031u - 19(a) Deraedt, C.; Pinaud, N.; Astruc, D. J. Am. Chem. Soc. 2014, 136, 12092– 12098(b) Deraedt, C.; Astruc, D. Acc. Chem. Res. 2014, 47, 494– 503[ACS Full Text
], [CAS], Google Scholar19bhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhslGgs77M&md5=b6385d76dcea5b842c9202b499c1e8d1"Homeopathic" Palladium Nanoparticle Catalysis of Cross Carbon-Carbon Coupling ReactionsDeraedt, Christophe; Astruc, DidierAccounts of Chemical Research (2014), 47 (2), 494-503CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)A review. Catalysis by palladium derivs. is now one of the most important tools in org. synthesis. Whether researchers design palladium nanoparticles (NPs) or nanoparticles occur as palladium complexes decomp., these structures can serve as central precatalysts in common carbon-carbon bond formation. Palladium NPs are also valuable alternatives to mol. catalysts because they do not require costly and toxic ligands. In this Account, we review the role of "homeopathic" palladium catalysts in carbon-carbon coupling reactions. Seminal studies from the groups of Beletskaya, Reetz, and de Vries showed that palladium NPs can catalyze Heck and Suzuki-Miyaura reactions with aryl iodides and, in some cases, aryl bromides at part per million levels. As a result, researchers coined the term "homeopathic" palladium catalysis. Industry has developed large-scale applications of these transformations. In addn., chemists have used Crooks' concept of dendrimer encapsulation to set up efficient nanofilters for Suzuki-Miyaura and selective Heck catalysis, although these transformations required high PdNP loading. With arene-centered, ferrocenyl-terminated dendrimers contg. triazolyl ligands in the tethers, we designed several generations of dendrimers to compare their catalytic efficiencies, varied the nos. of Pd atoms in the PdNPs, and examd. encapsulation vs. stabilization. The catalytic efficiencies achieved "homeopathic" (TON = 540 000) behavior no matter the PdNP size and stabilization type. The TON increased with decreasing the Pd/substrate ratio, which suggested a leaching mechanism. Recently, we showed that water-sol. arene-centered dendrimers with tri(ethylene glycol) (TEG) tethers stabilized PdNPs involving supramol. dendritic assemblies because of the interpenetration of the TEG branches. Such PdNPs are stable and retain their "homeopathic" catalytic activities for Suzuki-Miyaura reactions for months. (TONs can reach 2.7 × 106 at 80° for aryl bromides and similar values for aryl iodides at 28°) Sonogashira reactions catalyzed by these PdNPs are quant. with only 0.01%/Pd/mol substrate. Kato's group has reported remarkable catalytic efficiencies for mesoporous catalysts formed by polyamidoamine (PAMAM) dendrimer polymns. These and other mesoporous structures could allow for catalyst recycling, with efficiencies approaching the "homeopathic" behavior. In recent examples of Suzuki-Miyaura reactions of aryl chlorides, chemists achieved truly "homeopathic" catalysis when a surfactant such as a tetra-n-butylammonium halide or an imidazolium salt was used in stoichiometric quantities with substrate. These results suggest that the reactive halide anion of the salt attacks the neutral Pd species to form a palladate. In the case of aryl chlorides, the reaction may occur through the difficult, rate-limiting oxidative-addn. step. - 20(a) Myachina, G. F.; Konkova, T. V.; Korzhova, S. A.; Ermakova, T. G.; Pozdnyakov, A. S.; Sukhov, B. G.; Arsentev, K. Yu.; Likhoshvai, E. V.; Trofimov, B. A. Dokl. Chem. 2010, 431, 63– 64[Crossref], [CAS], Google Scholar20ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXjs1Onu7s%253D&md5=a662a80ff5369753cd429db80adce6a4Gold nanoparticles stabilized with water-soluble biocompatible poly(1-vinyl-1,2,4-triazole)Myachina, G. F.; Konkova, T. V.; Korzhova, S. 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In contrast, mismatches around the triazole linkage cause major structural and thermodn. perturbations. Thus, the biophys. results presented here, explain why only correct nucleotides are incorporated around the modified backbone during replication.
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Abstract

Scheme 1
Scheme 1. Synthesis of Ethynylbiferrocene 3Scheme 2
Scheme 2. Synthesis of the trz-BiFc-Functionalized Norbornene Monomer 7Figure 1

Figure 1. (a) Third generation Ru metathesis catalyst, Grubbs III (8) (b) CuACC catalyst copper [CuItren(CH2Ph)6][Br] (13).
Scheme 3
Scheme 3. ROMP Reaction of the trzBiFc Norbornene Monomer 7Scheme 4
Scheme 4. Synthesis of the Poly(trz-BiFc-methylstyrene) 14Scheme 5
Scheme 5. Synthesis of the Poly-trzBiFc-PEG Polymers 18 and 19Figure 2

Figure 2. CVs of (a) monomer 7, (b) polymer 9, and (c) progressive adsorption of polymer 9 onto a Pt electrode upon 20 scans around the BiFc potentials. Solvent: DCM; reference electrode: Ag; working and counter electrodes: Pt; scan rate: 0.2 V/s; supporting electrolyte: 0.1 M [n-Bu4N][PF6]. The wave at 0.0 V belongs to the internal reference FeCp*2.
Scheme 6
Scheme 6. Synthesis of Gold Vermicular AuNSs from Polymers 9, 10, and 14aScheme aPhotograph: isolated vermicular from the TEM analysis of AuNSs-14b.
Figure 3

Figure 3. (a) TEM analysis of mixed-valent biferrocenium polymer-stabilized AuNSs-14b at 0.5 μm; (b) size distribution of the AuNPs.
Figure 4

Figure 4. (a) AFM topography image (2 μm scale) of 10, (b) AFM topography image (270 nm scale) of AuNSs-10b, (c) AFM adhesion image (2 μm scale) of AuNSs-10b, and (d) AFM adhesion image (270 nm scale) of AuNSs-10b where three different regions A, B, and C are represented corresponding to three different force curves (Supporting Information).
Figure 5

Figure 5. (a) TEM of AuNPs-14c and (b) UV–vis spectrum of 14c (blue line). The violet line corresponds to the UV–vis spectrum after 5 min, and the red line is recorded after shaking of the sample. The photograph shows the flocculated AuNPs and their redissolution by shaking.
Figure 6

Figure 6. FT-IR (KBr) of (a) mixed-valent biferrocenium-stabilized AuNSs-14b, 844 cm–1 (νFc+) and 824 cm–1 (νFc), (b) polymer 14, 815 cm–1 (νFc).
Figure 7

Figure 7. (a) TEM analysis of AuNNs-18b at 200 nm, (b) UV–vis spectrum of AuNNs-18b peaking at 534 nm (plasmon band).
Scheme 7
Scheme 7. Synthesis of Gold Nano-Networks AuNNs-18bFigure 8

Figure 8. TEM analysis of 20b at 100 nm.
Figure 9

Figure 9. (a) TEM analysis of AgNSs-21b, (b) UV–vis spectrum of AgNSs-21b showing the plasmon band of AgNPs at λ = 434 nm and the biferrocenium band at λ = 630 nm.
Figure 10

Figure 10. (a) Modified Pt electrode of polymer 14 at various scan rates in a DCM solution containing only 0.1 M [n-Bu4N][PF6] as the supporting electrolyte; (b) intensity as a function of scan rate; linearity shows the expected behavior of an adsorbed polymer.
Figure 11

Figure 11. Voltammetric response of a platinum electrode modified with polymer 14, measured in H2O/0.1 M NaCl; scan rate: 50 mV s–1.
Figure 12

Figure 12. Recognition of ATP2– with a Pt modified electrode with polymer 14. (a) Modified electrode alone; (b) and (c) in the course of titration (the second wave is not represented as scanning until more positive potentials upon addition of ATP anions provokes instability of the electrode); (d) with an excess of [n-Bu4N]2[ATP]. Solvent: DCM; reference electrode: Ag; working and counter electrodes: Pt ; scan rate: 0.3 V/s ; supporting electrolyte: 0.1 M [nBu4N][PF6].
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], [CAS], Google Scholar7ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL2cXhtFOhurY%253D&md5=b9b11ac55d3a67c350104a0bc244399bFerrocene-mediated enzyme electrode for amperometric determination of glucoseCass, Anthony E. G.; Davis, Graham; Francis, Graeme D.; Hill, H. Allen O.; Aston, William J.; Higgins, I. John; Plotkin, Elliot V.; Scott, Lesley D. L.; Turner, Anthony P. F.Analytical Chemistry (1984), 56 (4), 667-71CODEN: ANCHAM; ISSN:0003-2700.The title electrode uses a substituted ferricinium ion as a mediator of electron transfer between immobilized glucose oxidase and a graphite electrode. A linear current response, proportional to the glucose concn. over a range commonly found in diabetic blood samples (1-30 mM), is obsd. Data are presented on the influence of oxygen, pH, and temp. upon the electrode. Results with clin. plasma and whole blood samples show good agreement with a std. method of anal.(b) Beer, P. D. Acc. Chem. Res. 1998, 31, 71– 80(c) Casado, C. M.; Cuadrado, I.; Moran, M.; Alonso, B.; Garcia, B.; Gonzales, B.; Losada, J. Coord. Chem. Rev. 1999, 185–6, 53– 79Google ScholarThere is no corresponding record for this reference.(d) Beer, P. D.; Gale, P. A. Angew. Chem., Int. Ed. 2001, 40, 486– 516[Crossref], [PubMed], [CAS], Google Scholar7dhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3MXhsVSrurc%253D&md5=2a491b49e9b3b9c21b9799d1e79ea7f3Anion recognition and sensing: the state of the art and future perspectivesBeer, Paul D.; Gale, Philip A.Angewandte Chemie, International Edition (2001), 40 (3), 486-516CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH)A review with 170 refs. Anion recognition chem. has grown from its beginnings in the late 1960s with pos. charged ammonium cryptand receptors for halide binding to, at the end of the millennium, a plethora of charged and neutral, cyclic and acyclic, inorg. and org. supramol. host systems for the selective complexation, detection, and sepn. of anionic guest species. Solvation effects and pH values play crucial roles in the overall anion recognition process. More recent developments include exciting advances in anion-templated syntheses and directed self-assembly, ion-pair recognition, and the function of anions in supramol. catalysis.(e) Casado, C. M.; Alonso, B.; Losada, J.; Garcia-Armada, M. P. In Designing Dendrimers; Campagna, S.; Ceroni, P.; Punteriero, F., Eds.; Wiley: Hoboken, NJ, USA, 2012; pp 219– 262.Google ScholarThere is no corresponding record for this reference.(f) Jimenez, A.; Armada, M. P. G.; Losada, L.; Villena, C.; AloAnso, B.; Casado, M. Sensors Actuators B-Chem. 2014, 190, 111– 119[Crossref], [CAS], Google Scholar7fhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhsleiur3F&md5=28bd1c43ee11f55b7f8543152f8a5772Amperometric biosensors for NADH based on hyperbranched dendritic ferrocene polymers and Pt nanoparticlesJimenez, Almudena; Armada, M. Pilar Garcia; Losada, Jose; Villena, Carlos; Alonso, Beatriz; Casado, Carmen M.Sensors and Actuators, B: Chemical (2014), 190 (), 111-119CODEN: SABCEB; ISSN:0925-4005. (Elsevier B.V.)The electrocatalytic performance of electrodes modified with Pt nanoparticles (PtNPs) and two dendritic hyperbranched carbosilane polymers, polydiallylmethylsilane (PDAMS) and polymethyldiundecenylsilane (PMDUS) with interacting ferrocenes, has been investigated for the NADH oxidn. The catalytic synergy of PtNPs with the interacting ferrocenes is discussed in relation with the polymer structure. This effect have allowed us to develop efficient biosensors capable of measuring NADH from +0.3 V (vs. SCE) providing a total protection vs. the poisoning of the electrodes. The polymer/PtNPs/Pt electrodes tolerate wide linear concn. ranges for NADH to 2.5 mM (R = 0.9979) and 2.1 mM (R = 0.99849), with detection limits of 4.78 μM and 6.18 μM and sensitivities of 68.24 and 40.21 μA mM-1 cm-2 for the PDAMS/PtNPs/Pt and PMDUS/PtNPs/Pt resp. In the light of the good results obtained, novel amperometric alc. biosensors were also successfully prepd. with alc. dehydrogenase (ADH). These devices showed more affinity for methanol than for ethanol, with a wide linear range to 30 mM and sensitivities of 0.957 and 0.756 μA mM-1 cm-2 for the ADH/PDAMS/PtNPs/Pt and ADH/PMDUS/PtNPs/Pt resp. The oxidn. potential of the NADH enzymically produced was neg. shifted to +0.25 V. - 8(a) Nguyen, P.; Gomez-Elipe, P.; Manners, I. Chem. Rev. 1999, 99, 1515– 1548(b) Abd-El-Aziz, A. S.; Bernardin, S. Coord. Chem. Rev. 2000, 203, 219– 267Google ScholarThere is no corresponding record for this reference.(c) Abd-El-Aziz, A. S.; Todd, E. K. Coord. Chem. Rev. 2003, 246, 3– 52Google ScholarThere is no corresponding record for this reference.(d) Macromolecules Containing Metal and Metal-Like Elements, Organoiron Polymers, Vol 2, Eds: Abd-El-Aziz, A. S.; Carraher, Jr., C. E.; Pittman, Jr., C. U.; Sheats, J. E.; Zeldin, M.; Wiley-Interscience: Hoboken: NJ, 2003.Google ScholarThere is no corresponding record for this reference.(e) Abd-El-Aziz, A. S.; Manners, I. J. Inorg. Organomet. Polym. 2005, 15, 157– 195[Crossref], [CAS], Google Scholar8ehttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXkvFCiu7s%253D&md5=26c6f693678629b6e908c6c0883fa363Neutral and cationic macromolecules based on iron sandwich complexesAbd-El-Aziz, Alaa S.; Manners, IanJournal of Inorganic and Organometallic Polymers and Materials (2005), 15 (1), 157-195CODEN: JIOPAY; ISSN:1574-1443. (Springer)A review on the synthesis, properties, and characterization of macromols. based on ferrocene or arene cyclopentadienyliron cations is presented. Ferrocene-based polymers in which the ferrocene moieties are in or pendent to the backbone are described, as well as, the use of arene cyclopentadienyliron complexes in the design of polymeric materials. The design of star-shaped macromols. and dendrimer materials that contain ferrocene and/or arene cyclopentadienyliron units are discussed as well.(f) Frontiers in Transition-Metal Containing Polymers, A. S. Abd-El-Aziz; Manners, I., Eds.; Wiley: New York, 2007.(g) Martinez, F. J.; Gonzalez, B.; Alonso, B.; Losada, J.; Garcia-Armada, M. P.; Casado, C. M. J. Inorg. Organomet. Polym. Mater. 2008, 18, 51– 58[Crossref], [CAS], Google Scholar8ghttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXptlensw%253D%253D&md5=ff5d83c4a602e62b3ec6808e20c29473Synthesis and redox properties of an electropolymerizable amido ferrocenyl pyrrole-functionalized dendrimerMartinez, Francisco J.; Gonzalez, Blanca; Alonso, Beatriz; Losada, Jose; Garcia-Armada, M. Pilar; Casado, Carmen M.Journal of Inorganic and Organometallic Polymers and Materials (2008), 18 (1), 51-58CODEN: JIOPAY; ISSN:1574-1443. (Springer)A novel ferrocenyl dendrimer functionalized with electrochem. polymerizable pyrrole substituents, with diaminobutane-based tetramido core, (DAB-dend)[(OC-η5-C5H4)Fe{η5-C5H4CONH(CH2)3NC4H4}]4 [1; H4DAB-dend = N,N,N',N'-tetrakis(3-aminopropyl)-1,4-butanediamine, NC4H4 = 1-pyrrolyl], was prepd. and characterized. A secondary reaction product, the dipyrrole deriv. [Fe{η5-C5H4CONH(CH2)3NC4H4}2] (2) also was isolated and used as a model to facilitate the characterization of 1. The mol. structure of 2 was detd. by single crystal x-ray diffraction studies. Glassy carbon electrodes have been successfully modified by electropolymn. of the pyrrole-functionalized derivs. 1 and 2, in dichloromethane/acetonitrile solns., resulting in visually detectable electroactive ferrocenyl polymer films persistently attached to the electrode surfaces. Osteryoung square wave voltammetry expts. (OSWV) showed that films of the electropolymd. dendrimer 1 (poly-1) senses H2PO4- in aq. soln. using Li[B(C6F5)4] as supporting electrolyte.
- 9(a) Manners, I. Science 2001, 294, 1664– 1666Google ScholarThere is no corresponding record for this reference.(b) Whittel, G. R.; Manners, I. Adv. Mater. 2007, 19, 3439– 3468Google ScholarThere is no corresponding record for this reference.(c) Hudson, Z.; Boot, C. E.; Robinson, M. E.; Rupar, P. A.; Winnink, M. A.; Manners, I. Nat. Chem. 2014, 6, 893– 898[Crossref], [PubMed], [CAS], Google Scholar9chttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhsFKms7rN&md5=d1c116fb9a6fb3dc89c228090cd899feTailored hierarchical micelle architectures using living crystallization-driven self-assembly in two dimensionsHudson, Zachary M.; Boott, Charlotte E.; Robinson, Matthew E.; Rupar, Paul A.; Winnik, Mitchell A.; Manners, IanNature Chemistry (2014), 6 (10), 893-898CODEN: NCAHBB; ISSN:1755-4330. (Nature Publishing Group)Recent advances in the self-assembly of block copolymers have enabled the precise fabrication of hierarchical nanostructures using low-cost soln.-phase protocols. However, the prepn. of well-defined and complex planar nanostructures in which the size is controlled in two dimensions (2D) has remained a challenge. Using a series of platelet-forming block copolymers, we have demonstrated through quant. expts. that the living crystn.-driven self-assembly (CDSA) approach can be extended to growth in 2D. We used 2D CDSA to prep. uniform lenticular platelet micelles of controlled size and to construct precisely concentric lenticular micelles composed of spatially distinct functional regions, as well as complex structures analogous to nanoscale single- and double-headed arrows and spears. These methods represent a route to hierarchical nanostructures that can be tailored in 2D, with potential applications as diverse as liq. crystals, diagnostic technol. and composite reinforcement.
- 10(a) Abakumova, L. G.; Abakumov, G. A.; Razuvaev, G. A. Dokl. Akad. Nauk SSSR 1975, 220, 1317– 1320Google ScholarThere is no corresponding record for this reference.(b) Huang, W. H.; Jwo, J. J. J. Chin, Chem. Soc. 1991, 38, 343– 350[CAS], Google Scholar10bhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK3MXlvVems7c%253D&md5=a9be599d17b047b946a48aced0e66a92Kinetics of the decomposition of ferrocenium ion and its derivativesHuang, Wen Hong; Jwo, Jing JerJournal of the Chinese Chemical Society (Taipei, Taiwan) (1991), 38 (4), 343-50CODEN: JCCTAC; ISSN:0009-4536.The first-order kinetics of the decompn. of ferrocenium ion (Fc+) and its substituted derivs. were studied in aq. sulfuric acid and in the presence of excess Ce(IV) ion. The obsd. first-order rate const. (kobs) is expressed as kobs = kd for the acyl-substituted ferrocenium ions and kobs = kd + kox[Ce(IV)0 for the unsubstituted and alkyl-substituted ferrocenium ions. Electron-donating alkyl substituents stabilize the ferrocenium ion whereas electron-withdrawing acyl substituents make it less stable. The order of relative stability toward decompn. is 1,1'-dimethyl Fc+ ≥ Bu Fc+ > 1,1-dimethylpropyl Fc+ > Fc+ >> formyl Fc+ > acetyl Fc+ >> benzoyl Fc+. A mechanism to interpret the kinetics is also given.(c) Zotti, G.; Schiavon, G.; Zecchin, S.; Berlin, A.; Pagani, G. Langmuir 1998, 14, 1728– 1733(d) Hurvois, J.-P.; Moinet, C. J. Organomet. Chem. 2005, 690, 1829– 1839[Crossref], [CAS], Google Scholar10dhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXivVSlsr4%253D&md5=5c92e755aaece09e230d85d7b6aed739Reactivity of ferrocenium cations with molecular oxygen in polar organic solvents: decomposition, redox reactions and stabilizationHurvois, J. P.; Moinet, C.Journal of Organometallic Chemistry (2005), 690 (7), 1829-1839CODEN: JORCAI; ISSN:0022-328X. (Elsevier B.V.)The behavior of chem. or electrochem. generated ferrocenium cations was studied in some polar org. solvents (DMF, DMSO, MeCN, acetone, CH2Cl2) under mol. oxygen. Adducts between oxygen and ferrocenium species can differently evolve according to the solvent (oxidizable or not) and the absence or the presence of another reagent. A rapid decompn. of ferrocenium cations is obsd. in the absence of another substrate. In the presence of some substrates and antioxidants, the stability of ferrocenium cations towards mol. oxygen notably increases and in some cases redox reactions take place with formation of ferrocene.
- 11(a) Cowan, D. O.; Kaufman, F. J. Am. Chem. Soc. 1970, 92, 219– 220(b) Cowan, D. O.; Kaufman, F. J. Am. Chem. Soc. 1971, 93, 3889– 3893(c) Levanda, C.; Cowan, D. O.; Bechgaard, K. J. Am. Chem. Soc. 1975, 97, 1980– 1981(d) Power, M. J.; Meyer, T. J. J. Am. Chem. Soc. 1978, 100, 4393– 4398Google ScholarThere is no corresponding record for this reference.
- 12(a) Robin, M. B.; Melvin, B.; Day, P. Adv. Inorg. Chem. Radiochem. 1967, 10, 247– 403[Crossref], [CAS], Google Scholar12ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaF1cXovF2isA%253D%253D&md5=2e720e6e07f03661b3eeb0fb2be3c598Mixed valence chemistry. A survey and classificationRobin, Melvin B.; Day, PeterAdvances in Inorganic Chemistry and Radiochemistry (1967), 10 (), 247-422CODEN: AICRAH; ISSN:0065-2792.A review. The theory of mixed valence effects is discussed in terms of the wave functions and mixed valence classification, mixed valence spectra, magnetism and electron transport, and mol. geometry. The mixed valence chemistry of the transition metals, Ga, In, Tl, Sn, Pb, P, As, Sb, Bi, the lanthanides, and the actinides is discussed. 820 references.(b) Allen, G. C.; Hush, N. S. Prog. Inorg. Chem. 1967, 8, 357– 390[Crossref], [CAS], Google Scholar12bhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaF1cXhtVSjsbk%253D&md5=0b16c71190cc7a504eee0068adcdca3eIntervalence-transfer absorption. I. Qualitative evidence for intervalence-transfer absorption in inorganic systems in solution and in the solid stateAllen, Geoffrey Charles; Hush, Noel S.Progress in Inorganic Chemistry (1967), 8 (), 357-89CODEN: PIOCAR; ISSN:0079-6379.The qual. evidence for intervalence-transfer absorption in inorg. systems in soln. and in the solid-state is reviewed. Sym. homonuclear, asym. homonuclear, and heteronuclear intervalence transfer are included. 116 references.(c) Richardson, D. E.; Taube, H. Coord. Chem. Rev. 1984, 60, 107– 129[Crossref], [CAS], Google Scholar12chttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL2MXht1Gjug%253D%253D&md5=f487a2ef7ad7c2f2cf6657f419237a73Mixed-valence molecules: electronic delocalization and stabilizationRichardson, David E.; Taube, HenryCoordination Chemistry Reviews (1984), 60 (), 107-29CODEN: CCHRAM; ISSN:0010-8545.A review with 40 refs.
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- 14Nijhuis, C. A.; Dolatowska, K. A.; Ravoo, B. J.; Huskens, J.; Reinhoudt, D. N. Chem.—Eur. J. 2007, 13, 69– 80[Crossref], [PubMed], [CAS], Google Scholar14https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXitlCisA%253D%253D&md5=6d639f0b3873cbe0e2bf64fba4ed24d7Redox-controlled interaction of biferrocenyl-terminated dendrimers with β-cyclodextrin molecular printboardsNijhuis, Christian A.; Dolatowska, Karolina A.; Ravoo, Bart Jan; Huskens, Jurriaan; Reinhoudt, David N.Chemistry--A European Journal (2007), 13 (1), 69-80CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)This paper describes the synthesis and electrochem. of biferrocenyl-terminated dendrimers and their β-cyclodextrin (β-CD) inclusion complexes in aq. soln. and at surfaces. Three generations of Poly(propyleneimine) (PPI) dendrimers, decorated with 4, 8, and 16 biferrocenyl (BFc) units, resp., were synthesized. A H2O-sol. BFc deriv. forms stable inclusion complexes with β-CD. The intrinsic binding const. is Ki = 2.5 × 104M-1. The BFc dendrimers were solubilized in H2O by complexation of the end groups with β-CD, resulting in large H2O-sol. supramol. assemblies. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) showed that all the end groups are complexed to β-CD. Adsorption of the dendrimers at self-assembled monolayers (SAMs) of heptathioether-functionalized β-CD on Au (mol. print-boards) resulted in stable monolayers of the dendrimers due to the formation of multivalent host-guest interactions between the BFc end groups of the dendrimers and the immobilized β-CD mols. The no. of interacting end groups is 3, 4, and 4 for dendrimers generations 1, 2, and 3, resp. The complexation of BFc to β-CD is sensitive to the oxidn. state of the BFc unit. Oxidn. of neutral BFc-Fe2(II,II) to the cationic, mixed-valence biferrocenium BFc-Fe2(II,III)+ resulted in dissocn. of the host-guest complexes. Scan-rate-dependent CV and DPV analyses of the dendrimers-β-CD assemblies immobilized at the β-CD host surface and in soln. revealed that the dendrimers are oxidized in 3 steps. First, the surface-β-CD-bound BFc moieties are oxidized to the mixed-valence state, Fe2(II,III)+, followed by the oxidn. of the nonsurface-interacting BFc groups to the Fe2(II,III)+ state. The 3rd step involves the oxidn. of all the BFc moieties to the Fe2(III,III)2+ state.
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- 18(a) Wang, Y.; Rapakousiou, A.; Chastanet, G.; Salmon, L.; Ruiz, J.; Astruc, D. Organometallics 2013, 32, 6136– 6146(b) Djeda, R.; Rapakousiou, A.; Liang, L.; Guidolin, N.; Ruiz, J.; Astruc, D. Angew. Chem., Int. Ed. 2010, 49, 8152– 8156Google ScholarThere is no corresponding record for this reference.(c) Astruc, D.; Liang, L.; Rapakousiou, A.; Ruiz, J. Acc. Chem. Res. 2012, 45, 630– 640[ACS Full Text
], [CAS], Google Scholar18chttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXhsF2lsb%252FM&md5=4e92ae2e4efc86a9c29587233d53db15Click Dendrimers and Triazole-Related Aspects: Catalysts, Mechanism, Synthesis, and Functions. A Bridge between Dendritic Architectures and NanomaterialsAstruc, Didier; Liang, Liyuan; Rapakousiou, Amalia; Ruiz, JaimeAccounts of Chemical Research (2012), 45 (4), 630-640CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)A review. One of the primary recent improvements in mol. chem. is the now decade-old concept of click chem. Typically performed as copper-catalyzed azide-alkyne (CuAAC) Huisgen-type 1,3-cycloaddns., this reaction has many applications in biomedicine and materials science. The application of this chem. in dendrimer synthesis beyond the zeroth generation and in nanoparticle functionalization requires stoichiometric use of the most common click catalyst, CuSO4·5H2O with sodium ascorbate. Efforts to develop milder reaction conditions for these substrates have led to the design of polydentate nitrogen ligands. Along these lines, we have described a new, efficient, practical, and easy-to-synthesize catalytic complex, [CuI(hexabenzyltren)]Br, 1 [tren = tris(2-aminoethyl)amine], for the synthesis of relatively large dendrimers and functional gold nanoparticles (AuNPs). This efficient catalyst can be used alone in 0.1% mol amts. for nondendritic click reactions or with the sodium-ascorbate additive, which inhibits aerobic catalyst oxidn. Alternatively, catalytic quantities of the air-stable compds. hexabenzyltren and CuBr added to the click reaction medium can provide analogously satisfactory results. Based on this catalyst as a core, we have also designed and synthesized analogous CuI-centered dendritic catalysts that are much less air-sensitive than 1 and are sol. in org. solvents or in water (depending on the nature of the terminal groups). These multivalent catalysts facilitate efficient click chem. and exert pos. dendritic effects that mimic enzyme activity. We propose a monometallic CuAAC click mechanism for this process. Although the primary use of click chem. with dendrimers has been to decorate dendrimers with a large no. of mols. for medicinal or materials purposes, we are specifically interested in the formation of intradendritic [1,2,3]-triazole heterocycles that coordinate to transition-metal ions via their nitrogen atoms. We describe applications including mol. recognition of anions and cations and the stabilization of transition metal nanoparticles according to a principle pioneered by Crooks with poly(amido amine) (PAMAM) dendrimers, and in particular, the control of structural and reactivity parameters in which the intradendritic [1,2,3]-triazoles and peripheral tripodal tri(ethylene glycol) termini play key roles in the click-dendrimer mediated synthesis and stabilization of gold nanoparticles (AuNPs). By varying these parameters, we have stabilized water-sol., weakly liganded AuNPs between 1.8 and 50 nm in size and have shown large differences in behavior between AuNPs and PdNPs. Overall, the new catalyst design and the possibilities of click dendrimer chem. introduce a bridge between dendritic architectures and the world of nanomaterials for multiple applications.(d) Poppitz, E. A.; Hildebrandt, A.; Korb, N.; Lang, H. J. Organomet. Chem. 2014, 752, 133– 140[Crossref], [CAS], Google Scholar18dhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXkvFOmug%253D%253D&md5=12e0681a15b684efda0c707984d6ba03Di(biferrocenyl)ethyne and -butadiyne: synthesis, properties and electron transfer studiesPoppitz, Elisabeth Andrea; Hildebrandt, Alexander; Korb, Marcus; Lang, HeinrichJournal of Organometallic Chemistry (2014), 752 (), 133-140CODEN: JORCAI; ISSN:0022-328X. (Elsevier B.V.)Di(biferrocenyl)ethyne (3) and -butadiyne (4) have been prepd. by Negishi, Eglinton and Sonogashira C,C cross-coupling reactions using 1'-iodo-1,1''-biferrocene (1) and 1'-ethynyl-1,1''-biferrocene (2) as starting materials. Compd. 4 was structurally analyzed by single crystal x-ray diffraction studies. The individual ferrocenyl units are all coplanar and anti-parallel oriented. Electrochem. measurements showed that all four ferrocenyl units can reversibly be oxidized. The electrochem. characteristics of these mols. represent a combination of the properties of biferrocene and the appropriate ferrocenyl analogs diferrocenyl ethyne and diferrocenyl butadiyne, resp. While the dicationic oxidn. state of both compds. showed characteristics of a charge transfer within the biferrocenium units, the tricationic form allows electron transfer through the (-C≡C-)n (n = 1, 2) functionalities. The obsd. inter-valence charge transfer (IVCT) interaction of 3 and 4 in any mixed-valent oxidn. state allowed the characterization of these species as class II systems according to Robin and Day. In situ IR spectroscopy of 3 and 4 showed that within 3n+ and 4n+ (n = 0, 2, 4) no νCC band is present, while 3+ and 33+ showed two νCC stretching vibrations due to Fermi resonance. Compd. 43+ exhibits only one sharp νCC frequency.(e) Rapakousiou, A.; Djeda, R.; Grillaud, M.; Li, N.; Ruiz, J.; Astruc, D. Organometallics 2014, DOI: 10.1021/om501031u - 19(a) Deraedt, C.; Pinaud, N.; Astruc, D. J. Am. Chem. Soc. 2014, 136, 12092– 12098(b) Deraedt, C.; Astruc, D. Acc. Chem. Res. 2014, 47, 494– 503[ACS Full Text
], [CAS], Google Scholar19bhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhslGgs77M&md5=b6385d76dcea5b842c9202b499c1e8d1"Homeopathic" Palladium Nanoparticle Catalysis of Cross Carbon-Carbon Coupling ReactionsDeraedt, Christophe; Astruc, DidierAccounts of Chemical Research (2014), 47 (2), 494-503CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)A review. Catalysis by palladium derivs. is now one of the most important tools in org. synthesis. Whether researchers design palladium nanoparticles (NPs) or nanoparticles occur as palladium complexes decomp., these structures can serve as central precatalysts in common carbon-carbon bond formation. Palladium NPs are also valuable alternatives to mol. catalysts because they do not require costly and toxic ligands. In this Account, we review the role of "homeopathic" palladium catalysts in carbon-carbon coupling reactions. Seminal studies from the groups of Beletskaya, Reetz, and de Vries showed that palladium NPs can catalyze Heck and Suzuki-Miyaura reactions with aryl iodides and, in some cases, aryl bromides at part per million levels. As a result, researchers coined the term "homeopathic" palladium catalysis. Industry has developed large-scale applications of these transformations. In addn., chemists have used Crooks' concept of dendrimer encapsulation to set up efficient nanofilters for Suzuki-Miyaura and selective Heck catalysis, although these transformations required high PdNP loading. With arene-centered, ferrocenyl-terminated dendrimers contg. triazolyl ligands in the tethers, we designed several generations of dendrimers to compare their catalytic efficiencies, varied the nos. of Pd atoms in the PdNPs, and examd. encapsulation vs. stabilization. The catalytic efficiencies achieved "homeopathic" (TON = 540 000) behavior no matter the PdNP size and stabilization type. The TON increased with decreasing the Pd/substrate ratio, which suggested a leaching mechanism. Recently, we showed that water-sol. arene-centered dendrimers with tri(ethylene glycol) (TEG) tethers stabilized PdNPs involving supramol. dendritic assemblies because of the interpenetration of the TEG branches. Such PdNPs are stable and retain their "homeopathic" catalytic activities for Suzuki-Miyaura reactions for months. (TONs can reach 2.7 × 106 at 80° for aryl bromides and similar values for aryl iodides at 28°) Sonogashira reactions catalyzed by these PdNPs are quant. with only 0.01%/Pd/mol substrate. Kato's group has reported remarkable catalytic efficiencies for mesoporous catalysts formed by polyamidoamine (PAMAM) dendrimer polymns. These and other mesoporous structures could allow for catalyst recycling, with efficiencies approaching the "homeopathic" behavior. In recent examples of Suzuki-Miyaura reactions of aryl chlorides, chemists achieved truly "homeopathic" catalysis when a surfactant such as a tetra-n-butylammonium halide or an imidazolium salt was used in stoichiometric quantities with substrate. These results suggest that the reactive halide anion of the salt attacks the neutral Pd species to form a palladate. In the case of aryl chlorides, the reaction may occur through the difficult, rate-limiting oxidative-addn. step. - 20(a) Myachina, G. F.; Konkova, T. V.; Korzhova, S. A.; Ermakova, T. G.; Pozdnyakov, A. S.; Sukhov, B. G.; Arsentev, K. Yu.; Likhoshvai, E. V.; Trofimov, B. A. Dokl. Chem. 2010, 431, 63– 64[Crossref], [CAS], Google Scholar20ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXjs1Onu7s%253D&md5=a662a80ff5369753cd429db80adce6a4Gold nanoparticles stabilized with water-soluble biocompatible poly(1-vinyl-1,2,4-triazole)Myachina, G. F.; Konkova, T. V.; Korzhova, S. A.; Ermakova, T. G.; Pozdnyakov, A. S.; Sukhov, B. G.; Arsentev, K. Yu.; Likhoshvai, E. V.; Trofimov, B. A.Doklady Chemistry (2010), 431 (1), 63-64CODEN: DKCHAY; ISSN:0012-5008. (Pleiades Publishing, Ltd.)Gold nanoparticles are used in medicine for providing the transport of therapeutic substances or genes into the cell by endocytosis. The authors report the synthesis of new water-sol. composites contg. gold nanoparticles stabilized with poly(1-vinyl-1,2,4-triazole). Elemental and at. absorption analyses show that the nanocomposites contain 4-6% of gold. The obtained nanocomposites are promising for the targeted delivery of pharmaceuticals and for the development of diagnostic system and nanosensor devices.(b) Oldham, E. D.; Seelam, S.; Lema, C.; Agulera, R. J.; Fiegel, J.; Rankin, S. E.; Knutson, B. L.; Lehmler, H. Carbohydr. Res. 2013, 379, 68– 77Google ScholarThere is no corresponding record for this reference.(c) Dallmann, A.; El-Sagheer, A. 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In contrast, mismatches around the triazole linkage cause major structural and thermodn. perturbations. Thus, the biophys. results presented here, explain why only correct nucleotides are incorporated around the modified backbone during replication.
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Supporting Information
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ARTICLE SECTIONSSpectroscopic data for all the complexes and NMR, IR, near-IR, UV–vis. spectra and CVs. This material is available free of charge via the Internet at http://pubs.acs.org.
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