（联吡啶）（三联吡啶）钌（II）和（联吡啶）铱（III）络合物的氰化物桥联双核络合物中的高效能量转移和金属偶联,Inorganic Chemistry

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（联吡啶）（三联吡啶）钌（II）和（联吡啶）铱（III）络合物的氰化物桥联双核络合物中的高效能量转移和金属偶联
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2016-05-23 00:00:00 , DOI: 10.1021/acs.inorgchem.5b02919
Kevin Barthelmes _{1,

2} , Michael Jäger _{1,

2} , Joachim Kübel _{3,

4} , Christian Friebe _{1,

2} , Andreas Winter _{1,

2} , Maria Wächtler ₃ , Benjamin Dietzek _{2,

3,

4} , Ulrich S. Schubert _{1,

2}

Affiliation

我们报告了一系列具有广义通式[Ir（（R ₂）₂ -ppy）₂（CN）（μ-CN）Ru（bpy）（tpy）的氰化物桥接的异双核铱（III）-钌（II）配合物-R ₁）] PF ₆（ppy ＝ 2-苯基吡啶，bpy ＝ 2，2′-联吡啶，并且tpy ＝ 2，2′：6′，2″-叔吡啶）。在吸电子（例如-F，-Br，-CHO）和-给体（例如-Me）和扩展的π共轭基团在多个位置变化的情况下分析了结构，光谱和电化学性质。总共已经制备了十种双核配合物和合适的模型配合物。在这些配合物中，基于铱（III）的发射几乎完全被猝灭，并且仅观察到基于钌（II）的发射，这表明向Ru中心的有效能量转移。钌中心氧化后，氟化配合物2在近红外区域表现出宽间隔的电荷转移跃迁。根据Robin-Day分类，将复合物分配给弱耦合的II类系统。通过密度泛函理论（DFT）和随时间变化的DFT计算来评估电子结构，以证实实验数据。

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

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.

更新日期：2016-05-23

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