摘要
制备并表征了一系列以柔韧烷氧链相连的自由双卟啉及其锌配合物，以１ＨＮＭＲ考察了烷氧链长度及锌离子对双卟啉构象平衡的影响．结果表明，双卟啉存在开放式及闭合式构象平衡，随烷氧链的增长，构象平衡由开放式向闭合式移动，当链上碳原子数为４时最有利于双卟啉形成闭合式构象．锌离子与卟啉环配位后未改变构象平衡趋势．应用ＩＲ谱研究了双卟啉环间π－π相互作用，利用荧光光谱考察了双卟啉环间单重态能量转移。
A series of porphyrin dimers and their zinc complex covalently linked with \{_O(CH\-2)\-nO_\}(n: 2_10) chain were synthesized and characterized. Their steady\|state fluorescence spectra show the existence of intramolecular energy transfer processes in these free\|base porphyrin dimers. C\-4 free dimer has the greatest efficiency of energy transfer. By using IR and \{\}\+1H NMR methods, the relationship between the conformation equilibrium and the length of the alkoxyl chain, the metal complexation was studied. With the increase of the length of the chain, the conformation equilibrium of porphyrin dimers moves to the closed conformation, the chain length of C\-4 dimer was suitable to form the closed conformation. The metallation with zinc ion increases the magnitude of \| interaction of two porphyrin rings while it does not affect the conformation equilibrium of porphyrin dimers.
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
1999年第3期333-338,共6页
Chemical Journal of Chinese Universities
基金
国家自然科学基金
广东省自然科学基金
南京大学配位化学国家重点实验室资助
