摘要
本文研究了Co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)、Zn(Ⅱ)原卟啉Ⅸ二甲酯(PP)络合物的共振拉曼光谱。其结构灵敏带频率次序;Ni>(Ⅱ)Co>(Ⅱ)Cu>(Ⅱ)Zn(Ⅱ)。紫外光谱λ_(max)次序:Ni(Ⅱ)<Co(Ⅱ)<Cu(Ⅱ)<Zn(Ⅱ)。对主要拉曼带作了经验归属。用金属离子半径和d_(x2-y2)电子排斥作用解释了拉曼结构灵敏带和紫外光谱随金属离子不同的变化规律,支持了“心膨胀”机理。还研究了Cupp和C(?)的退偏比色散性。
Resonance Raman spectra (RRS) of Co(11), Ni(11), Cu(11), Zn(11) ProtoPorphyrin Ⅸ bimethyl ester (PP) complexes are studied using uifferent excitation lines of an argon laser. Raman frequencies of their structure-sensitive RR banbs decrease in the order of Ni (Ⅱ)>Co(Ⅱ)>Cu(Ⅱ)>Zn(Ⅱ); anb the λ_(max) of the UV absorption bands increase in the order of Ni (Ⅱ) <Co (Ⅱ)<Cu(Ⅱ)<Zn(Ⅱ). The empirical assignments of the major RR bands are given. The radii of metal-ions and the repellent effect of d_(x^2-y^2) electrons on the porphvrin ring are used to explain the variation of the structure-sensitive RR bands and UV absorption bands of the complexes with different metal-ions. This work supports the 'core expansion' mechanism. The effect of spin state on the RRS of metalloporphyrins can also be explained by the repellent effect of metallic d_(x^2-y^2) electrons. The dispersion of depolarization ratio in CoPP and CuPP is studied.
出处
《光谱学与光谱分析》
SCIE
EI
CAS
CSCD
北大核心
1989年第1期6-1,共1页
Spectroscopy and Spectral Analysis
基金
中国科学院科学基金
