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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Tuning the excited-state deactivation pathways of dinuclear ruthenium(ii) 2,2 '-bipyridine complexes through bridging ligand design
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Tuning the excited-state deactivation pathways of dinuclear ruthenium(ii) 2,2 '-bipyridine complexes through bridging ligand design

机译：通过桥接配体设计调整二核钌（II）2,2'-脂吡啶配合物的激发态失活途径

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摘要

A detailed photophysical investigation of two dinuclear ruthenium(ii) complexes is reported. The two metallic centers were coordinated to a bis-2,2 '-bipyridine bridging ligand, connected either through thepara(L-p,D-p) or themetaposition (L-m,D-m). The results obtained herein were compared to the prototypical [Ru(bpy)(3)](2+)parent compound. The formation of dinuclear complexes was accompanied by the expected increase in molar absorption coefficients,i.e.12 000 M(-1)cm(-1), 17 000 M(-1)cm(-1), and 22 000 M(-1)cm(-1)at the lowest energy MLCT(max)transition for [Ru(bpy)(3)](2+),D-m and D-p respectively. The L-p bridging ligand resulted in a ruthenium(ii) dinuclear complex that absorbed more visible light, and had a longer-lived and more delocalized excited-state compared to a complex with theL(m)bridging ligand. Variable temperature measurements provided valuable information about activation energies to the uppermost(3) MLCT state and the metal-centered ((MC)-M-3) state, often accompanied by irreversible ligand-loss chemistry. At 298 K, 48% of [Ru(bpy)(3)](2+)* excited-state underwent deactivation through the(3)MC state, whereas this deactivation pathway remained practically unpopulated (<0.5%) in both dinuclear complexes.
机译：报道了两种二核钌（II）配合物的详细的光物理研究。两种金属中心与双-2,2'-β-Biphyridine桥接配体配位，通过ThePara（L-P，D-P）或TheTeTaposition（L-M，D-M）连接。将本文获得的结果与原型[Ru（BPY）（3）]（2+）母体化合物进行比较。双核复合物的形成伴随着以摩尔吸收系数的预期增加，IE12 000 M（-1）厘米（-1），17 000 M（-1）厘米（-1），和22 000 M（-1 ）CM（-1）在最低能量MLCT（MAX）过渡分别用于[Ru（BPY）（3）]（2 +），DM和DP的转变。 L-P桥接配体导致钌（II）二核复合物，其吸收更可见光，与与桥接配体的复合物相比具有更长寿命和更疏散的激发态。可变温度测量为最高（3）MLCT状态和金属中心（（MC）-M-3）状态提供了有关激活能量的有价值的信息，通常伴随着不可逆的配体损失化学。在298 k，48％的[ru（bpy）（3）]（2 +）*兴奋状态通过（3）mc状态进行失活，而这种失活途径在二维核复合物中仍然存在实际上未占（<0.5％） 。

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