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用密度泛函理论的B3LYP法,将中位-四[二-(3,4-羧甲氧基)苯基]卟啉及结合Re=O分子的几何构型优化,初步理论研究其前沿轨道和能量等。证明,与单独的卟吩环相比,T_(3,4)CPP的卟吩环平面性良好,环上的结构参数变化很小;Re=O与T_(3,4)CPP卟吩环的结合能明显大于与T_(3,4)CPP侧链羧基的结合能,且前者所形成配合物的稳定性显然高于后者,说明T_(3,4)CPP与~(188)Re=O结合的位点应在卟吩环上,而不在侧链羧基上。T_(3,4)CPP卟吩环结合Re=O而形成配合物的结构参数,与Vicente等Zn-卟啉衍生物的测定值相近。在卟吩环上配位时,T_(3,4)CPP卟吩环上的电荷重新分布,卟吩环碳原子的电子向4个氮原子转移:配位后,卟吩环的几何构型略收缩(0.14 A-0.19 A)和马鞍形扭转(5.7°)。
The density functional theory of B3LYP method, the median - tetra [di - (3,4-carboxymethoxy) phenyl] porphyrin and Re = O molecular geometry optimization, preliminary theoretical study of its frontier orbit And energy and so on. It was proved that the porphyrin ring of T_ (3,4) CPP had a good planarity and a small change in the structural parameters on the ring compared with the corresponding porphin ring. Re = O and T_ (3,4) CPP The binding energy of the complexes was significantly higher than that of the side chain carboxyl group of T_ (3,4) CPP. The stability of the complex formed by the former was obviously higher than that of the latter, indicating that T_ (3,4) CPP and ~ (188) Re = O The binding site should be on the porphin ring, not on the pendant carboxyl group. The structural parameters of T_ (3,4) CPP porphyrin ring combined with Re = O are similar to those of Zn-porphyrin derivatives such as Vicente et al. When coordinating with the porphine ring, the charge on the porphyrin ring of T_ (3,4) CPP is redistributed and the electrons of the carbon atom of the porphyrin ring transfer to the four nitrogen atoms: after coordination, the geometrical configuration of the porphin ring Slight contraction (0.14 A-0.19 A) and saddle twist (5.7 °).