Ivanovo State University of Chemistry and Technology, Research Institute of Chemistry of Macroheterocyclic Compounds, 153000 Ivanovo, Russia.
Int J Mol Sci. 2020 Apr 22;21(8):2923. doi: 10.3390/ijms21082923.
Electronic and geometric structures of Ca(II) and Zn(II) complexes with porphyrazine (Pz) and tetrakis(1,2,5-thiadiazole)porphyrazine (TTDPz) were investigated by density functional theory (DFT) calculations and compared. The perimeter of the coordination cavity was found to be practically independent on the nature of a metal and a ligand. According to the results of the natural bond orbital (NBO) analysis and quantum theory of atoms in molecules (QTAIM) calculations, Ca-N bonds possess larger ionic contributions as compared to Zn-N. The model electronic absorption spectra obtained with the use of time-dependent density functional theory (TDDFT) calculations indicate a strong bathochromic shift (~70 nm) of the Q-band with a change of Pz ligand by TTDPz for both Ca and Zn complexes. Additionally, CaTTDPz was synthesized and its electronic absorption spectrum was recorded in pyridine and acetone.
采用密度泛函理论（DFT）计算对钙（II）和锌（II）与卟嗪（Pz）和四（1,2,5-噻二唑）卟嗪（TTDPz）的配合物的电子和几何结构进行了研究，并进行了比较。发现配位腔的周长实际上与金属和配体的性质无关。根据自然键轨道（NBO）分析和分子中的原子量子理论（QTAIM）计算的结果，与 Zn-N 相比，Ca-N 键具有更大的离子贡献。使用含时密度泛函理论（TDDFT）计算获得的模型电子吸收光谱表明，对于 Ca 和 Zn 配合物，Q 带的红移（~70nm）很大，卟嗪配体由 TTDPz 取代。此外，还合成了 CaTTDPz，并在吡啶和丙酮中记录了其电子吸收光谱。
