Efficient Energy Transfer and Metal Coupling in Cyanide-Bridged Heterodinuclear Complexes Based on (Bipyridine)(terpyridine)ruthenium(II) and (Phenylpyridine)iridium(III) Complexes

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• 作者：Kevin Barthelmes ; Michael Jäger ; Joachim Kübel ; Christian Friebe ; Andreas Winter ; Maria Wächtler ; Benjamin Dietzek ; Ulrich S. Schubert
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：June 6, 2016
• 年：2016
• 卷：55
• 期：11
• 页码：5152-5167
• 全文大小：826K
• 年卷期：0
• ISSN：1520-510X

文摘

We report a series of cyanide-bridged, heterodinuclear iridium(III)–ruthenium(II) complexes with the generalized formula [Ir((R₂)₂-ppy)₂(CN)(μ-CN)Ru(bpy)(tpy-R₁)]PF₆ (ppy = 2-phenylpyridine, bpy = 2,2′-bipyridine, and tpy = 2,2′:6′,2″-terpyridine). The structural, spectroscopic, and electrochemical properties were analyzed in the context of variation of the electron-withdrawing (e.g., −F, −Br, −CHO) and -donating (e.g., −Me) and extended π-conjugated groups at several positions. In total, ten dinuclear complexes and the appropriate model complexes have been prepared. The iridium(III)-based emission is almost fully quenched in these complexes, and only the ruthenium(II)-based emission is observed, which indicates an efficient energy transfer toward the Ru center. Upon oxidation of the Ru center, the fluorinated complexes 2 exhibit a broad intervalence charge-transfer transition in the near-infrared region. The complexes are assigned to a weakly coupled class II system according to the Robin–Day classification. The electronic structure was evaluated by density functional theory (DFT) and time-dependent DFT calculations to corroborate the experimental data.