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Redox‐Robust Pentamethylferrocene Polymers and Supramolecular Polymers, and Controlled Self‐Assembly of Pentamethylferricenium Polymer‐Embedded Ag, AgI, and Au Nanoparticles
Author(s) -
Gu Haibin,
Ciganda Roberto,
Castel Patricia,
Vax Amélie,
Gregurec Danijela,
Irigoyen Joseba,
Moya Sergio,
Salmon Lionel,
Zhao Pengxiang,
Ruiz Jaime,
Hernández Ricardo,
Astruc Didier
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201503248
Subject(s) - romp , norbornene , supramolecular polymers , polymer , polymerization , metathesis , ruthenium , redox , monomer , supramolecular chemistry , nanoparticle , grubbs' catalyst , cyclic voltammetry , polymer chemistry , ring opening metathesis polymerisation , chemistry , hexafluorophosphate , materials science , catalysis , nanotechnology , organic chemistry , electrochemistry , ionic liquid , crystal structure , electrode
We report the first pentamethylferrocene (PMF) polymers and the redox chemistry of their robust polycationic pentamethylferricenium (PMFium) analogues. The PMF polymers were synthesized by ring‐opening metathesis polymerization (ROMP) of a PMF‐containing norbornene derivative by using the third‐generation Grubbs ruthenium metathesis catalyst. Cyclic voltammetry studies allowed us to determine confidently the number of monomer units in the polymers through the Bard–Anson method. Stoichiometric oxidation by using ferricenium hexafluorophosphate quantitatively and instantaneously provided fully stable (even in aerobic solutions) blue d 5 Fe III metallopolymers. Alternatively, oxidation of the PMF‐containing polymers was conducted by reactions with Ag I or Au III , to give PMFium polymer‐embedded Ag and Au nanoparticles (NPs). In the presence of I 2 , oxidation by using Ag I gave polymer‐embedded Ag/AgI NPs and AgNPs at the surface of AgI NPs. Oxidation by using Au III also produced an Au I intermediate that was trapped and characterized. Engineered single‐electron transfer reactions of these redox‐robust nanomaterial precursors appear to be a new way to control their formation, size, and environment in a supramolecular way.