| 手性络合物[M(bpy)_2(phen)]~(2+)和[M(phen)_2(bpy)]~(2+)(M=Ru,Os)圆二色谱的理论解析 |
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| 引用本文： | 高小丽,王越奎,王炎,贾杰,苏晓玲.手性络合物[M(bpy)_2(phen)]~(2+)和[M(phen)_2(bpy)]~(2+)(M=Ru,Os)圆二色谱的理论解析[J].中国科学:化学,2011(7):1145-1155. |
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| 作者姓名： | 高小丽 王越奎 王炎 贾杰 苏晓玲 |
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| 作者单位： | 化学生物学与分子工程教育部重点实验室山西大学分子科学研究所;吕梁学院化学化工系; |
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| 基金项目： | 国家自然科学基金(20673069); 山西省自然科学基金(2007011021)资助 |
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| 摘 要： | 应用密度泛函理论,在B3LYP/LanL2DZ水平上对C2对称性的混配络合物M(bpy)2(phen)]2+和M(phen)2(bpy)]2+(M=Ru、Os;bpy=2,2'-bipyridine;phen=1,10-phenanthroline)在水溶液中的几何构型进行了优化,并用TDDFT/B3LYP方法和相同的基组计算了其激发能、旋转强度和振子强度,绘制了相应的圆二色谱(CD).在分析有关跃迁性质的基础上,对实验圆二色谱的谱带进行了明确的解析和指认,同时讨论了短波区激子裂分的规律性.结果表明:四种络合物在长波区(λ>320nm)的CD吸收带主要是由d-π*跃迁产生的荷移谱带;短波区(λ<320nm)则是配体上平行于长轴的π-π*跃迁产生的激子耦合带,且对于Λ构型表现为正的手性激子裂分.其中,M(bpy)2(phen)]2+只显示出正负两个激子带,分属于联吡啶和邻菲咯啉配体;而M(phen)2(bpy)]2+则有三个激子带,其中左侧的两个(一负一正)属于邻菲咯啉配体,右侧的正带则属于联吡啶配体.此外,尽管激子耦合属于远程相互作用,但用TDDFT计算的激子裂分样式仍是正确的.这些结论对于深入理解有...
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| 关 键 词： | 钌、锇的混配络合物 ECD谱理论解析 TDDFT计算 手征光学性质 |
Theoretical analysis of the CD spectra and chiroptical properties of [M(bpy)_2(phen)]~(2+) and [M(phen)_2(bpy)]~(2+) (M=Ru,Os) chelates |
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| GAO XiaoLi ,WANG YueKui ,WANG Yan ,JIA Jie & SU XiaoLing Key Laboratory of Chemical Biology , Molecular Engineering,Ministry of Education.Theoretical analysis of the CD spectra and chiroptical properties of [M(bpy)_2(phen)]~(2+) and [M(phen)_2(bpy)]~(2+) (M=Ru,Os) chelates[J].Scientia Sinica Chimica,2011(7):1145-1155. |
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| Authors: | GAO XiaoLi WANG YueKui WANG Yan JIA Jie & SU XiaoLing Key Laboratory of Chemical Biology Molecular Engineering Ministry of Education |
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| Institution: | GAO XiaoLi 1,WANG YueKui 1,WANG Yan 2,JIA Jie 1 & SU XiaoLing 1 1 Key Laboratory of Chemical Biology and Molecular Engineering,Ministry of Education,Institute of Molecular Science,Shanxi University,Taiyuan 030006,China 2 Department of Chemistry and Chemical Engineering,LvLiang University,Lvliang 033000,China |
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| Abstract: | Calculations of the excitation energies,oscillator and rotational strengths,and the CD spectra of the chelates M(bpy)2(phen)]2+ and M(phen)2(bpy)]2+ (M=Ru,Os;bpy=2,2'-bipyridine;phen=1,10-phenanthroline) have been performed at the TDDFT/B3LYP/LanL2DZ//DFT/B3LYP/LanL2DZ level including solvent effects.The calculated CD spectra are in good agreement with the observed ones.Detailed analysis for the dominant transitions reveals that the CD bands in the long wavelength region (320-700 nm) are dominated by the ... |
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| Keywords: | Ru（Ⅱ）/Os（Ⅱ） chelates with different ligands theoretical analysis of ECD TDDFT calculation chiroptical properties |
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