title: Electrografting of diazonium-functionalized polyoxometalates: synthesis, immobilisation and electron-transfer characterisation from glassy carbon.
abstract: 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.
authors.affiliation: Institut 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).
authors.forename: Corentin
authors.initials: C
authors.lastname: Rinfray
authors.forename: Guillaume
authors.initials: G
authors.lastname: Izzet
authors.forename: Jean
authors.initials: J
authors.lastname: Pinson
authors.forename: Sarra
authors.initials: S
authors.lastname: Gam Derouich
authors.forename: Jean-Jacques
authors.initials: JJ
authors.lastname: Ganem
authors.forename: Catherine
authors.initials: C
authors.lastname: Combellas
authors.forename: Frédéric
authors.initials: F
authors.lastname: Kanoufi
authors.forename: Anna
authors.initials: A
authors.lastname: Proust
keywords: diazonium grafting; electron transfer; electron transport; polyoxometalates; surface immobilization