界面缩聚法合成聚卟啉金属配合物及其表征

Interfacical Polycondensation Prepared with Polymeric Porphyrin Complexes and Characterization

利用对苯二甲酰氯交联meso-5,10,15,20-四(对羟基苯基)卟啉单体制备了聚卟啉配体及其Co(Ⅱ)、Mn(Ⅱ)和Zn(Ⅱ)金属配合物,并对聚卟啉配体和金属配合物进行了红外光谱、扫描电镜和X射线光电子能谱分析。结果表明,卟啉单体是典型的晶体结构,而发生界面聚合过程中以平面二维方式进行,形成膜状聚合物;当金属离子与卟啉形成配合物后,其中一对N—H键中质子被配位金属取代,N1S轨道的电子结合能变化小于0.2eV,环中另外两个N原子与配位金属形成σ配位键,导致配位金属M2p3/2的电子结合能变化大于0.5eV,引起了卟啉环内层电子密度的变化。

The polymeric porphyrin and Co（ Ⅱ ） ,Mn（Ⅱ） and Zn（Ⅱ） complexes have prepared with meso-5, 10, 15, 20-tetra （hydroxyphenyl） porphyrin and terephthaloyl chloride by interfacical polycondensation. Their structures were charactered with infrared spectra （IR）, scanning electron microscope （SEM） and X-ray photoelectron spectroscopic （XPS） analysis. It showed that the film of the polymeric porphyrin was synthesis by two-dimensional polymeric method, compared with the typical crystal structure of porphyrin unit. When the metalloporphyrins were synthesis, a pair of proton in which N-H bond is replaced by metal coordination, there Nas orbital electron binding energy changes less than 0.2eV. The other two N atom of the porphyrin ring are coordinated to the metal coordination formation σ coordination bond, effect of the M2p3/2of metal coordination electron binding energy changes more than 0.5eV. The porphyrin ring inner electron density was changed when metal ion coordination to ligand L.