@article { ISI:000330202300039,
	title = {Intramolecular and Lateral Intermolecular Hole Transfer at the Sensitized TiO2 Interface},
	journal = {JOURNAL OF THE AMERICAN CHEMICAL SOCIETY},
	volume = {136},
	number = {3},
	year = {2014},
	month = {JAN 22},
	pages = {1034-1046},
	abstract = {Characterization of the redox properties of TiO2 interfaces sensitized to visible light by a series of cyclometalated ruthenium polypyridyl compounds containing both a terpyridyl ligand with three carboxylic acid/carboxylate or methyl ester groups for surface binding and a tridentate cyclometalated ligand with a conjugated triarylamine (NAr3) donor group is described. Spectroelectrochemical studies revealed non-Nernstian behavior with nonideality factors of 1.37 +/- 0.08 for the Ru-III/II couple and 1.15 +/- 0.09 for the NAr3 center dot+/0 couple. Pulsed light excitation of the sensitized thin films resulted in rapid excited-state injection (k(inj) > 10(8) s(-1)) and in some cases hole transfer to NAr3 {[}TiO2(e(-))/Ru-III-NAr3 -> TiO2(e(-))/Ru-II-NAr3 center dot+]. The rate constants for charge recombination {[}TiO2(e(-))/Ru-III-NAr3 -> TiO2/Ru-II-NAr3 or TiO2(e(-))/Ru-II-NAr3 center dot+ -> TiO2/Ru-II-NAr3] were insensitive to the identity of the cyclometalated compound, while the open-circuit photovoltage was significantly larger for the compound with the highest quantum yield for hole transfer, behavior attributed to a larger dipole moment change (Delta mu = 7.7 D). Visible-light excitation under conditions where the Ru-III centers were oxidized resulted in injection into TiO2 {[}TiO2/Ru-III-NAr3 + h nu -> TiO2(e(-))/Ru-III-NAr3 center dot+] followed by rapid back interfacial electron transfer to another oxidized compound that had not undergone excited-state injection {[}TiO2(e(-))/Ru-III-NAr3 -> TiO2/Ru-II-NAr3]. The net effect was the photogeneration of equal numbers of fully reduced and fully oxidized compounds. Lateral intermolecular hole hopping (TiO2/Ru-II-NAr3 + TiO2/Ru-III-NAr3 center dot+ -> 2TiO(2)/Ru-III-NAr3) was observed spectroscopically and was modeled by Monte Carlo simulations that revealed an effective hole hopping rate of (130 ns)(-1).},
	issn = {0002-7863},
	doi = {10.1021/ja410647c},
	author = {Hu, Ke and Robson, Kiyoshi C. D. and Beauvilliers, Evan E. and Schott, Eduardo and Zarate, Ximena and Arratia-Perez, Ramiro and Berlinguette, Curtis P. and Meyer, Gerald J.}
}
