title: Strongly Coupled Cyclometalated Ruthenium Triarylamine Chromophores as Sensitizers for DSSCs.
abstract: A series of anchor-functionalized cyclometalated bis(tridentate) ruthenium(II) triarylamine hybrids [Ru(dbp-X)(tctpy)](2-) [2 a](2-) -[2 c](2-) (H3 tctpy=2,2';6',2''-terpyridine-4,4',4''-tricarboxylic acid; dpbH=1,3-dipyridylbenzene; X=N(4-C6 H4 OMe)2 ([2 a](2-) ), NPh2 ([2 b](2-) ), N-carbazolyl [2 c](2-) ) was synthesized and characterized. All complexes show broad absorption bands in the range 300-700 nm with a maximum at about 545 nm. Methyl esters [Ru(Me3 tctpy)(dpb-X)](+) [1 a](+) -[1 c](+) are oxidized to the strongly coupled mixed-valent species [1 a](2+) -[1 c](2+) and the Ru(III) (aminium) complexes [1 a](3+) -[1 c](3+) at comparably low oxidation potentials. Theoretical calculations suggest an increasing spin delocalization between the metal center and the triarylamine unit in the order [1 a](2+) <[1 b](2+) <[1 c](2+) . Solar cells were prepared with the saponified complexes [2 a](2-) -[2 c](2-) and the reference dye N719 as sensitizers using the I3 (-) /I(-) couple and [Co(bpy)3 ](3+/2+) and [Co(ddpd)2 ](3+/2+) couples as [B(C6 F5 )4 ](-) salts as electrolytes (bpy=2,2'-bipyridine; ddpd=N,N'-dimethyl-N,N'-dipyridin-2-yl-pyridine-2,6-diamine). Cells with [2 c](2-) and I3 (-) /I(-) electrolyte perform similarly to cells with N719. In the presence of cobalt electrolytes, all efficiencies are reduced, yet under these conditions [2 c](2-) outperforms N719.
authors.affiliation: Institute of Inorganic Chemistry and Analytical Chemistry, Johannes Gutenberg-University of Mainz, Duesbergweg 10-14, 55128, Mainz, Germany), Fax: (+49) 6131-39-27-277.|Graduate School Materials Science in Mainz, Staudingerweg 9, 55128, Mainz, Germany.
authors.forename: Christoph
authors.initials: C
authors.lastname: Kreitner
authors.affiliation: Institute of Inorganic Chemistry and Analytical Chemistry, Johannes Gutenberg-University of Mainz, Duesbergweg 10-14, 55128, Mainz, Germany), Fax: (+49) 6131-39-27-277.
authors.forename: Andreas K C
authors.initials: AK
authors.lastname: Mengel
authors.affiliation: The Department of Energy Engineering and Center for, Next Generation Dye-Sensitized Solar Cells, Hanyang University, 222 Wangsimni-ro, Seongdong-gu, Seoul, 133-791, Korea.
authors.forename: Tae Kyung
authors.initials: TK
authors.lastname: Lee
authors.affiliation: The Department of Energy Engineering and Center for, Next Generation Dye-Sensitized Solar Cells, Hanyang University, 222 Wangsimni-ro, Seongdong-gu, Seoul, 133-791, Korea.
authors.forename: Woohyung
authors.initials: W
authors.lastname: Cho
authors.affiliation: The National Creative Research Initiative Center for Intelligent, Hybrids, School of Chemical and Biological Engineering, Seoul, National University, 1 Gwanak-ro, Gwanak-gu, Seoul, 151-744, Korea.
authors.forename: Kookheon
authors.initials: K
authors.lastname: Char
authors.affiliation: The Department of Energy Engineering and Center for, Next Generation Dye-Sensitized Solar Cells, Hanyang University, 222 Wangsimni-ro, Seongdong-gu, Seoul, 133-791, Korea.
authors.forename: Yong Soo
authors.initials: YS
authors.lastname: Kang
authors.affiliation: Institute of Inorganic Chemistry and Analytical Chemistry, Johannes Gutenberg-University of Mainz, Duesbergweg 10-14, 55128, Mainz, Germany), Fax: (+49) 6131-39-27-277. katja.heinze@uni-mainz.de.
authors.forename: Katja
authors.initials: K
authors.lastname: Heinze
keywords: cobalt electrolytes; cyclometalated complexes; dye-sensitized solar cells; mixed valency; ruthenium