Physicochemical Analysis of Ruthenium(II) Sensitizers of 1,2,3-Triazole-Derived Mesoionic Carbene and Cyclometalating Ligands

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• 作者：Stephan Sinn ; Benjamin Schulze ; Christian Friebe ; Douglas G. Brown ; Michael J?ger ; Esra Altunta? ; Joachim Kübel ; Oliver Guntner ; Curtis P. Berlinguette ; Benjamin Dietzek ; Ulrich S. Schubert
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：February 17, 2014
• 年：2014
• 卷：53
• 期：4
• 页码：2083-2095
• 全文大小：654K
• ISSN：1520-510X

文摘

A series of heteroleptic bis(tridentate) ruthenium(II) complexes bearing ligands featuring 1,2,3-triazolide and 1,2,3-triazolylidene units are presented. The synthesis of the C^N^N-coordinated ruthenium(II) triazolide complex is achieved by direct C鈥揌 activation, which is enabled by the use of a 1,5-disubstituted triazole. By postcomplexation alkylation, the ruthenium(II) 1,2,3-triazolide complex can be converted to the corresponding 1,2,3-triazolylidene complex. Additionally, a ruthenium(II) complex featuring a C^N^C-coordinating bis(1,2,3-triazolylidene)pyridine ligand is prepared via transmetalation from a silver(I) triazolylidene precursor. The electronic consequences of the carbanion and mesoionic carbene donors are studied both experimentally and computationally. The presented complexes exhibit a broad absorption in the visible region as well as long lifetimes of the charge-separated excited state suggesting their application in photoredox catalysis and photovoltaics. Testing of the dyes in a conventional dye-sensitized solar cell (DSSC) generates, however, only modest power conversion efficiencies (PCEs).