【摘要】 对比 Fe Pc研究了标题配合物 Fe Pz(dtn) 4和 Fe Pz(dcdtn) 4的电子结构及吸收光谱 .发现 Fe Pc大环外围硫原子及氯原子取代均导致吸收光谱的 B带与 Q带能差减小 .UHF- ZINDO/1全优化计算证明 :标题配合物和 Fe Pc分子的基态均为自旋三重态 ,且三者基态与最低能量自旋单态的能差相近 ,基态结合能的绝对值按 Fe Pc>Fe Pz(dtn) 4>Fe Pz(dcdtn) 4顺序依次减小 ,铁原子的净电荷按 Fe Pc<Fe Pz(dtn) 4<Fe Pz(dcdtn) 4顺序依次增多 .多组态 CI研究表明 ,三者的吸收带在本质上属于 Pz大环的π→π*跃迁 ,且伴随有弱的 d- d跃迁 .更多还原

【Abstract】 The electronic structure and absorption spectra of the title complexes FePz(dtn) 4 and FePz(dcdtn) 4 compared with FePc are investigated by the geometry optimizations in the UHF\|ZINDO/1 and the CI calculations of multi\|configurations in the RHF\|ZINDO/S method. It has been found that the molecular ground state of three complexes is spin triplet state, and the binding energy of the molecule and the net charge of the central Fe is incremental in the order FePc<FePz(dtn) 4<FePz(dcdtn) 4. The wavelength and oscillator strength of calculated transition is in conformity with the observed absorption spectra in the solutions. The energy of the Q\|band is incremental in the order FePc<FePz(dtn) 4<FePz(dcdtn) 4.更多还原