Redox-Robust Pentamethylferrocene Polymers and Supramolecular Polymers, and Controlled Self-Assembly of Pentamethylferricenium Polymer-Embedded Ag, AgI, and Au Nanoparticles.
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 I2 , 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.
Key Laboratory of Leather Chemistry and, Engineering of Ministry of Education, Sichuan University, Chengdu 610065 (P. R. China).|ISM, UMR CNRS No. 5255, Univ. Bordeaux, 33405 Talence Cedex (France).
Haibin
H
Gu
ISM, UMR CNRS No. 5255, Univ. Bordeaux, 33405 Talence Cedex (France).|Facultad de Química de San Sebastián, Universidad del País Vasco, Apdo. 1072, 20080 San Sebastián (Spain).
Roberto
R
Ciganda
ISM, UMR CNRS No. 5255, Univ. Bordeaux, 33405 Talence Cedex (France).
Patricia
P
Castel
LCPO, UMR CNRS No. 5629, University of Bordeaux, 33607 Pessac Cedex (France).
Amélie
A
Vax
CIC biomaGUNE, Unidad Biosuperficies, Paseo Miramón No. 182, Edif "C", 20009 Donostia-San Sebastián (Spain).
Danijela
D
Gregurec
CIC biomaGUNE, Unidad Biosuperficies, Paseo Miramón No. 182, Edif "C", 20009 Donostia-San Sebastián (Spain).
Joseba
J
Irigoyen
CIC biomaGUNE, Unidad Biosuperficies, Paseo Miramón No. 182, Edif "C", 20009 Donostia-San Sebastián (Spain).
Sergio
S
Moya
LCC, UPR CNRS No. 8241, 205 Route de Narbonne, 31077 Toulouse Cedex (France).
Lionel
L
Salmon
Science and Technology on Surface Physics and Chemistry Laboratory, PO Box 718-35, Mianyang 621907, Sichuan (P. R. China).
Pengxiang
P
Zhao
ISM, UMR CNRS No. 5255, Univ. Bordeaux, 33405 Talence Cedex (France).
Jaime
J
Ruiz
Facultad de Química de San Sebastián, Universidad del País Vasco, Apdo. 1072, 20080 San Sebastián (Spain).
Ricardo
R
Hernández
ISM, UMR CNRS No. 5255, Univ. Bordeaux, 33405 Talence Cedex (France). d.astruc@ism.u-bordeaux1.fr.
Didier
D
Astruc
cyclic voltammetry; metallopolymers; nanoparticles; pentamethylferrocene; ring-opening-metathesis polymerization