折叠型双银配合物电子结构与相关性质  

Electronic Structure and Related Properties of di-NuclearSilver Complex with Folded Structure

作　　者：郑康成[1] 匡代彬[1] 沈勇[1] 康北笙[1] 

机构地区：[1]中山大学化学与化学工程学院,广州510275

出　　处：《高等学校化学学报》2002年第4期670-673,共4页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:29671035)资助.

摘　　要：在密度泛函Ｂ３ＬＹＰ/ＬａｎＬ ２ＤＺ的水平上,对具有π－π弱相互作用调控的折叠型银配合物Ａｇ２(ＭＰＴＱ)_２^(２＋)进行计算研究．探讨该配合物的电子结构、成键特征、π－π弱相互作用机理、电荷布居及其相关性质．计算结果表明,Ａｇ…Ａｇ之间存在弱的直接相互作用,ＨＯＭＯ主要布居在配体中芳香环的σ－ｐ轨道、Ｓ的σ－ｐ轨道及与Ｓ相连的Ｃ１２的Ｓ轨道上,ＬＵＭＯ主要布居在配体中芳香环的π*－ｐ轨道上,基态电子光谱主要是配体中的ｎ→π*跃迁产生的电荷转移光谱．论文还讨论了分子间π－π弱相互作用的本质及活性部位等．计算结果能较好地解释实验现象与规律．Theoretical studies on the weak π-π interaction-controlled di-nuclear Ag (I) complexAg,(MPTQ)_2^(2+) with folded structure were carried out with DFT mbthod at B3LYP/LanL 2DZ level. Theelectronic structure of the complex, the characteristic of its bonding, the mechanism of π-π interactions,the atomic net charge populations and the related properties of the complex have been investigated. The re-sults show that there is a weak direct π-π interaction between the two silver atoms in the complex. TheHOMO of the complex is mainly populated on the π-p orbitals of the aromatic rings, the σ-p orbitals of Satoms and s orbitals of C12 atoms, whereas the LUMO is predominantly located on the π*-p orbitals of thearomatic rings. The electronic spectrum of the ground state of the complex may be predicted to assign tothe n→π* CT band from the n-p orbitals of S and s orbitals of C12 to the π* -p orbitals of the aromaticrings. In addition, the mechanism of π-π interactions among the complex molecules was also further ex-plored. The calculation results can be better used to explain the experimental phenomena and regularities.

关 键 词：银配合物 8-(2-吡啶甲巯基)喹啉 π-π弱相互作用 密度泛函法 电子结构 量子化学 分子间相互作用 

分 类 号：O614.122[理学—无机化学] O641.121[理学—化学]