单臂冠醚-金属卟啉配合物的合成与表征

Synthesis and Characterization of Mono-arm Crown Ether-metalloporphyrin Complexes

利用磺酰氯键将苯并15-冠-5和5-(2-羟基苯基)-10,15,20-三(4-硝基苯基)交联,合成了单臂冠醚—卟啉配体(CNTPP)及其金属配合物(CNTPPMn和CNTPPCo)。通过红外光谱、紫外吸收光谱与光电子能谱对化合物和配合物进行结构分析表明,在489cm-1和480cm-1出现M-N键的吸收峰,在1360cm-1和1363cm-1处有S=O键吸收峰。配位中心离子进入卟啉环后引起配合物CNTPPM分子的对称性提高,使Sorct带发生位移,且N原子与金属离子形成配位键后,其中一对N电子结合能升高,另外一对N原子下降,且导致配合物中M2p3/2的电子结合能变大。

The mono-arm crown ether-metalloporphyrin ligand（CNTPP） and its complexes（CNTPPMn and CNTPPCo） were prepared with benzo15-crown-5 and 5-（2-hydroxyphenyl）-10,15,20-（4-nitro-phenyl） Cobalt（Ⅱ） prophyrin by terephthaloyl chloride.The structures were charactered with infrared spectra（IR）,Ultraviolet and Visible Spectroscopy（UV-Vis） and X-ray photoelectron spectroscopic（XPS） analysis.The results showed that the M-N and S=O bond absorption peak appeared at 489cm-1,480cm-1,1360cm-1 and 1363cm-1 respectively.The porphyrin ring molecular symmetry was increased with the metal ions added into porphyrin ligand,and the sorct band of UV-Vis absorption was changed,in which a pair of N atom electron binding energy increased,but another decreased with the M-N bond was formed.Furthermore,metalions（M2p3/2） electron binding energy was increased.