单核锌双卟啉配合物构象平衡的理论研究及光谱分析  

Theoretic Conformation Analysis and Spectroscopic Properties of Alkoxy Linked Dimeric Porphyrins

作　　者：任奇志[1] 朱志昂[2] 王曙光[1] 计亮年[3] 陈荣悌[2] 

机构地区：[1]上海交通大学化学化工学院,上海200240 [2]南开大学化学系,天津3000712 [3]中山大学化学系,广州5102753

出　　处：《无机化学学报》2002年第4期335-341,共7页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金资助项目(No.29871018)。

摘　　要：合成了一系列以不同长度柔韧链相连的p/p型单核锌双卟啉配合物。选用Tripos力场,利用分子动力学模拟退火和分子力学构象搜索相结合的方法对该系列双卟啉进行了能量优化和构象分析。理论计算结果表明:该类双卟啉稳定存在的最低能量构象为叠合式,最高能量构象为伸展式,并存在一系列的中间能量构象;双卟啉分子内π-π作用和能量转移与双卟啉存在的两种主要构象密切相关;分析了分子内π-π作用的本质。运用不同光谱测试手段验证了理论计算结果:利用可见和相应二阶导数吸收光谱研究了双卟啉主要存在的叠合式和伸展式构象,通过红外光谱观察了对双卟啉构象和卟啉环间π-π作用较为敏感的吸收谱带;利用荧光光谱计算了双卟啉的分子内能量转移效率。A series of zinc porphyrin dimers have been synthesized and characterized. Conformation analysis and π πinteraction estimated value were performed using molecular mechanics conformation search and molecular dynamics simulated annealing methods (in Tripos force field, SYBYL computation). Conformation equilibrium, intramolecular π πinteraction and energy transfer have also been investigated in detail via various spectroscopic methods: Visible adsorption and second derivative adsorption, IR, and fluorescence spectrum. The theoretic viable lowest energy conformations greatly coincide with spectroscopic data. The porphyrin dimers were mainly existed in extended and folded conformations, as the increase of the side chain length, the π πfolded degree and intramolecular energy transfer increase gradually.

关 键 词：单核锌卟啉配合物 构象分析 分子力学 Tripos力场 构象平衡 光谱分析 表征 分子动力学 

分 类 号：O614.241[理学—无机化学] O657.3[理学—化学]