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Synthesis and Redox Activity of “Clicked” Triazolylbiferrocenyl Polymers, Network Encapsulation of Gold and Silver Nanoparticles and Anion Sensing

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ISM, UMR CNRS No. 5255, Université de Bordeaux, 33405 Talence Cedex, France
CIC biomaGUNE, Unidad Biosuperficies, Paseo Miramón 182, Edif. “C”, 20009 Donostia-San Sebastián, Spain
§ Laboratoire de Chimie de Coordination UPR CNRS No. 8241, 31077 Toulouse Cedex, France
Cite this: Inorg. Chem. 2015, 54, 5, 2284–2299
Publication Date (Web):February 13, 2015
https://doi.org/10.1021/ic5028916
Copyright © 2015 American Chemical Society
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Abstract

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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.

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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.

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Cited By


This article is cited by 12 publications.

  1. Asanda C. Matsheku, Richard Tia, Munaka C. Maumela, Banothile C. E. Makhubela. Ferrocenylimine Palladium (II) Complexes: Synthesis, Characterization and Application in Mizoroki-Heck and Suzuki-Miyaura Cross-Coupling Reactions. Catalysts 2021, 11 (7) , 755. https://doi.org/10.3390/catal11070755
  2. Xiong Liu, Amalia Rapakousiou, Christophe Deraedt, Roberto Ciganda, Yanlan Wang, Jaime Ruiz, Haibin Gu, Didier Astruc. Multiple applications of polymers containing electron-reservoir metal-sandwich complexes. Chemical Communications 2020, 56 (77) , 11374-11385. https://doi.org/10.1039/D0CC04586A
  3. Chip Nataro. Ferrocene: To Infinity and Back Again. 2019,,https://doi.org/10.1016/B978-0-12-409547-2.14671-2
  4. Li Zhao, Qiangjun Ling, Xiong Liu, Chaodong Hang, Qiuxia Zhao, Fangfei Liu, Haibin Gu. Multifunctional triazolylferrocenyl Janus dendron: Nanoparticle stabilizer, smart drug carrier and supramolecular nanoreactor. Applied Organometallic Chemistry 2018, 32 (2) https://doi.org/10.1002/aoc.4000
  5. Ileana Dragutan, Valerian Dragutan, Albert Demonceau. Organometallic Polymers by Ring-Opening Metathesis Polymerization (ROMP) Reactions. 2018,,https://doi.org/10.1016/B978-0-12-409547-2.14232-5
  6. Didier Astruc. Why is Ferrocene so Exceptional?. European Journal of Inorganic Chemistry 2017, 2017 (1) , 6-29. https://doi.org/10.1002/ejic.201600983
  7. James W. Herndon. The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2015. Coordination Chemistry Reviews 2016, 329 , 53-162. https://doi.org/10.1016/j.ccr.2016.08.007
  8. A.I. Gopalan, N. Muthuchamy, S. Komathi, K-P Lee. A novel multicomponent redox polymer nanobead based high performance non-enzymatic glucose sensor. Biosensors and Bioelectronics 2016, 84 , 53-63. https://doi.org/10.1016/j.bios.2015.10.079
  9. Ileana Dragutan, Valerian Dragutan, Petru Filip, Bogdan C. Simionescu, Albert Demonceau. ROMP Synthesis of Iron-Containing Organometallic Polymers. Molecules 2016, 21 (2) , 198. https://doi.org/10.3390/molecules21020198
  10. Ileana Dragutan, Valerian Dragutan, Albert Demonceau. Editorial of Special Issue Ruthenium Complex: The Expanding Chemistry of the Ruthenium Complexes. Molecules 2015, 20 (9) , 17244-17274. https://doi.org/10.3390/molecules200917244
  11. Wolf Peter Fehlhammer, Wolfgang Beck. Azide Chemistry - An Inorganic Perspective, Part II [‡] [3+2]-Cycloaddition Reactions of Metal Azides and Related Systems. Zeitschrift für anorganische und allgemeine Chemie 2015, 641 (10) , 1599-1678. https://doi.org/10.1002/zaac.201500165
  12. Ileana Dragutan, Valerian Dragutan, Bogdan C Simionescu, Albert Demonceau, Helmut Fischer. Recent advances in metathesis-derived polymers containing transition metals in the side chain. Beilstein Journal of Organic Chemistry 2015, 11 , 2747-2762. https://doi.org/10.3762/bjoc.11.296

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