title: Polypyridyl Ru(II)-derivatized polypropylacrylate polymer with a terminal water oxidation catalyst. Application of reversible addition-fragmentation chain transfer polymerization.
abstract: A Ru(II) polypyridyl-derivatized polypropylacrylate end-capped with a water-oxidation-catalyst (WOC) has been synthesized by using reversible addition-fragmentation chain transfer polymerization (RAFT) followed by click reaction and end-group functionalization. In cyclic voltammograms in propylene carbonate, chromophore oxidation occurs at 1.27 V vs. NHE and the Ru(III/II) wave for the catalyst at 0.84 V vs. NHE. Upon excitation of the Ru(II) chromophore, excited-state energy migration occurs by site-to-site, -Ru(II)*- → -Ru(II)-, energy transfer hopping along the polymer chain, in part, reaching the terminal catalyst site where -Ru(II)*- → -Ru(II)-OH2(2+) energy transfer is favored by ΔG(en) = -2100 cm(-1). Added MV(2+) as an electron transfer acceptor oxidizes the -Ru(II)*- excited state on the polymer to Ru(III), -Ru(II)*- + MV(2+) → -Ru(III)- + MV(+), and ultimately, the catalyst, by site-to-site electron transfer hopping and oxidation, [Formula: see text]. Oxidation is followed by relatively slow, diffusional back electron transfer from MV˙(+) to Ru(III) sites on the polymer chain. The mixed chromophore-catalyst polymer is a water oxidation catalyst with potential for enhanced light harvesting and water oxidation.
authors: Department of Chemistry, University of North Carolina at Chapel Hill, CB3290, Chapel Hill, North Carolina 27599, USA. tjmeyer@unc.edu.
authors: Zhen
authors: Z
authors: Fang
authors: Akitaka
authors: A
authors: Ito
authors: Hanlin
authors: H
authors: Luo
authors: Dennis L
authors: DL
authors: Ashford
authors: Javier J
authors: JJ
authors: Concepcion
authors: Leila
authors: L
authors: Alibabaei
authors: Thomas J
authors: TJ
authors: Meyer