含席夫碱桥联配体的双核金属钌配合物的合成及其性能研究(英文) |
Synthesis and Properties of Dinuclear Ruthenium Complexes with Schiff Base Bridging Ligands |
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摘要: 合成了3种双核钌配合物[Ru(bpy)2]2{[(PyCHN)-Ph-O-C6H4-]2R}(ClO4)4,bpy=2,2′-联吡啶,PyCHN=N-2-吡啶亚甲基,R=无(1),-C(CH3)2 (2),-SO2 (3)并进行了有关表征。电化学研究表明:配合物3的ΔE和Kc值最大, 说明苯环和硫原子之间存在着较强的(p(π)-d)π相互作用,有助于获得较强的金属-金属相互作用。配合物1,2,3都有混合价,通过Hush方程可以得到Vab的值大概为320~420 cm-1。这些结果表明:Schiff碱作为桥配体对于调配金属-金属相互作用并将其作为分子导线起着特殊的作用。 |
关键词: 双核钌配合物 金属-金属相互作用 分子导线 |
基金项目: |
Abstract: Binuclear ruthenium complexes [Ru(bpy)2]2{[(PyCHN)-Ph-O-C6H4-]2R}(ClO4)4, where bpy=2,2′-bipyridine, PyCHN=N-2-pyridylmethylene, R=none for 1, -C(CH3)2 for 2 and -SO2 for 3, have been prepared and characterized. Electrochemical studies reveal that the ΔE and Kc for complexes 1, 2 and 3 are surprisingly and unprecedentedly large. However, the complex 3 gives larger ΔE and Kc. It is suggested that the strong (p(π)-d)π interactions between the phenyl rings and the sulfur atom should be helpful to achieve stronger metal-metal interaction. For mixed-valence species of complexes 1, 2 and 3, Vab can be obtained by Hush equation with a value of 320~420 cm-1. These results indicate that the Schiff base bridging ligands show particular efficiency for mediating the metal-metal interactions and for using as molecular wires. |
Keywords: binuclear ruthenium complexes, metal-metal interaction, molecular wires |
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张 燕,熊 碧,蔡 苹,程功臻.含席夫碱桥联配体的双核金属钌配合物的合成及其性能研究(英文)[J].无机化学学报,2012,28(11):2437-2443. |
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