Theoretical Studies on the Cu-Cu Interaction and Stability of [Cu_a(Ph_2Ppy)_b(CH_3CN)_c]~(a+) (a=1~2,b=1~3,c=0~2) |
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作者姓名: | XIE Mei-Xiang XU Xuan HUANG Xiao-Xuan |
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作者单位: | XIE Mei-Xiang,HUANG Xiao-Xuan(School of Chemistry & Environment,South China Normal University,Guangzhou 510006,China);XU Xuan(School of Chemistry & Environment,South China Normal University,Guangzhou 510006,China ;Key Laboratory of Electrochemical Technology on Energy Storage and Power Generation of Guangdong Higher Education Institutes,Guangzhou 510006,China) |
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基金项目: | Supported by the Natural Science Foundation of Guangdong Province (No. 5005938), and Research Project of Ministry of Education and Guangdong Province, China (2007A090302046) |
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摘 要: | To study the Cu-Cu interaction and stability of the title complexes,the structures of complexes Cu(Ph2Ppy)(CH3CN)]+ 1,Cu(Ph2Ppy)]+ 2,Cu2(Ph2Ppy)2(CH3CN)2]2+ 3,Cu2(Ph2Ppy)2(CH3CN)]2+ 4,Cu2(Ph2Ppy)2]2+ 5 and Cu2(Ph2Ppy)3(CH3CN)]2+ 6 were calculated by density functional theory PBE0 method,and the following conclusions can be drawn:(1) There is no orbital overlapping between two Cu atoms,indicating no Cu-Cu orbital interaction exists in complexes 3~6.Due to a breakdown of the closed shell configuration of Cu atoms,the weak Cu-Cu interactions result from the 3dCu → 4sCu' charge-transfer in 4~6.The Cu-Cu interaction strength follows 5 6 4,implying that there are stronger Cu-Cu interactions in the complexes with fewer CH3CN or more Ph2Ppy ligands.(2) The calculated interaction energies suggest that the coordination of Cu to Ph2Ppy is stronger than that to CH3CN.In 3~6,there are weaker interactions between Cu and CH3CN or Ph2Ppy in the complexes with more CH3CN or Ph2Ppy ligands.(3) The P-Cu and N-Cu interactions are much stronger than the Cu-Cu interaction,so we mainly attribute the stabilities of the binuclear complexes to the eight-membered rings Cu2P2N2C2.
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关 键 词: | 轨道相互作用 铜配合物 稳定性 乙腈 密度函数理论 相互作用强度 相互作用能 弱相互作用 |
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