新型吡啶基修饰的尾式卟啉的合成及性质

Synthesis and Properties of Novel Porphyrin Modified by Pyridine Derivative

报道了一种新型尾式锌卟啉(o-PyOC6H12OTPPZn)的合成及表征,采用紫外-可见光谱滴定法对该化合物与5种吡啶类小分子间的轴向配位反应的热力学性质进行了研究.轴配体系的热力学数据显示,5种吡啶类配体的平衡常数按K(4-M ePy)>K(Py)>K(3-M ePy)>K(2,4,6-triM ePy)>K(2-M ePy)依次减小,吡啶类小分子对主体的配位能力按4-M ePy>Py>3-M ePy>2,4,6-triM ePy>2-M ePy依次减弱,同时分子模拟的理论研究得到了与实验完全一致的结果.通过Z-扫描实验对该化合物的非线性光学性质的研究表明,该样品具有较强的反饱和吸收特征.

A new kind of tailed zinc porphyrin modified by pyridine derivative （o-PyOC6H12 OTPPZn） was synthesized and characterized by elementary analysis, UV-Vis, I H NMR, IR, and MS spectra. The axial coordination reaction was studied between o-PyOC6H120TPPZn and pyridine derivatives by UV-Vis spectra titration. The binding constants decreased in the order of K （ 4-MePy ） 〉 K （ Py ） 〉 K （ 3-MePy ） 〉 K （ 2,4,6-triMePy） 〉 K（2-MePy） for pyridine derivatives. The results show that the capability of axial ligands decreased in the sequence of 4-MePy 〉 Py 〉 3-MePy 〉 2,4,6-triMePy 〉 2-MePy. Moreover, the lowest energy conformations of the complexes between the zinc porphyrin and pyridine derivatives were obtained by simulated annealing and the results explained the experiment results well. The nonlinear optical property of o-PyOC6H12OTPPZn was investigated by Z-scan experiment. Reverse saturated absorption of the compound was observed.