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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 p / p mononuclear zinc bis-porphyrin complexes with different lengths of flexible chains were synthesized. The Tripos force field was chosen to optimize the energy and conformational analysis of this series of bis-porphyrin by the combination of molecular dynamics simulation annealing and molecular mechanics conformation search. The theoretical calculations show that the lowest energy conformations of this type of bis-porphyrin are superposed, the highest energy conformation is extended, and a series of intermediate energy conformations exist. The intramolecular π-π interaction and the energy transfer of bis The two main conformations of the presence of porphyrin are closely related; the nature of the π-π interaction within the molecule is analyzed. The results of theoretical calculations were validated by different spectral test methods. The dominant and dominant conformations of bis-porphyrin were studied by visible and corresponding second-order derivative absorption spectroscopy. The conformation of bis-porphyrin and the interaction between porphyrin ring π-π role of the more sensitive absorption bands; calculated by fluorescence spectroscopy intramolecular energy transfer efficiency of the porphyrin.