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Chemistry. 2013 Oct 4;19(41):13838-46. doi: 10.1002/chem.201302304. Epub 2013 Sep 3.

Electrografting of diazonium-functionalized polyoxometalates: synthesis, immobilisation and electron-transfer characterisation from glassy carbon.

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  • 1Institut Parisien de Chimie Moléculaire, UMR CNRS 7201-UPMC Univ Paris 06, Université Pierre et Marie Curie, 4 place Jussieu, case courrier 42, 75252 Paris Cedex 05 (France).


Polyoxometalates (POMs) are attractive candidates for the rational design of multi-level charge-storage materials because they display reversible multi-step reduction processes in a narrow range of potentials. The functionalization of POMs allows for their integration in hybrid complementary metal oxide semiconductor (CMOS)/molecular devices, provided that fine control of their immobilisation on various substrates can be achieved. Owing to the wide applicability of the diazonium route to surface modification, a functionalized Keggin-type POM [PW11 O39 {Ge(p-C6 H4 -CC-C6 H4 -${{\rm N}{{+\hfill \atop 2\hfill}}}$)}](3-) bearing a pending diazonium group was prepared and subsequently covalently anchored onto a glassy carbon electrode. Electron transfer with the immobilised POM was thoroughly investigated and compared to that of the free POM in solution.

Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.


diazonium grafting; electron transfer; electron transport; polyoxometalates; surface immobilization

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