3 years ago

Bonding and Electronic Properties of Linear Diethynyl Oligothienoacene-Bridged Diruthenium Complexes and Their Oxidized Forms

Bonding and Electronic Properties of Linear Diethynyl Oligothienoacene-Bridged Diruthenium Complexes and Their Oxidized Forms
Fuxing Zhang, František Hartl, Ming-Xing Zhang, Sheng Hua Liu, Daizhi Kuang, Ya-Ping Ou, Jing Zhang
Localization of the highest occupied molecular orbital of the parent diruthenium complexes on the redox-noninnocent oligothienoacene bridge core with strong participation of the ethynyl linkers and a limited contribution from the metallic termini makes the initial one-electron oxidation symmetrical. The remarkable appearance of a dual IR ν(C≡C) absorption in the cationic complexes is ascribed to a vibronic coupling of the IR-forbidden νs(C≡C) mode of the oxidized −[C≡C−core−C≡C]+− bridge to the low-lying π−π*(intrabridge)/metal-to-ligand charge-transfer electronic transition in the near-to-mid-IR spectral region.

Publisher URL: http://dx.doi.org/10.1021/acs.inorgchem.7b01433

DOI: 10.1021/acs.inorgchem.7b01433

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