四溴四苯基卟啉及其金属配合物的电子结构和四溴四苯基卟啉Ni(II)的晶体结构

本文合成了7, 8, 17, 18-四溴-5, 10, 15, 20-四苯基-21, 23(H)-卟啉(H~2TPPBr~4)及其金属配合物MTPPBr~4M=Cu(II), Ni(II), Co(II)和Zn(II)]。测定了它们的可见紫外光谱和循环伏安, 用四轨道模型(Four Orbital Model)计算了MTPPBr~4的相对前线轨道, 并解释了配合物的可见紫外光谱及电化学性质。测定了NiTPPBr~4的晶体结构, 晶体属单斜晶系, 空间群C2/c, a=2.6077(7),b=1.0414(4), c=1.9312(3)nm, β=137.1(7)°, Z=4, 最后偏离因子R=0.067, 晶体结构直接证明了卟啉亲电溴化反应具有区域选择性, 四个溴分布在相对两个吡咯环上。

The electronic structure of tetrabromotetraphenylporphyrin and its metalloporphyrins [M=Cu(II), Co(II), Ni(II), Zr(II)] and the crystal structure of Ni(II)TPPBr~4

MTPPBr4 (M = Cu, Co, Ni, Zn) were synthesized. Their UV-visible spectra and cyclic voltammetry were determine The relative energy of frontier orbital of metalloporphyrins, which explained the characters of UV-visible spectra and electrochem., were calculated according to four orbital parameters. The crystal structure of NiTPPBr4 was determine by a CAD4 diffractometer. Crystallog. parameters were as follows: monoclinic, space group C2/c with a 2.6077(7), b 1.0414(4), c 1.9312(3) nm; b 137.1(7)? Z = 4, F(000) = 2048, final R = 0.067. This structure directly verified that electrophilic bromination occurred regiospecifically at the antipodal pyrrolenic ring of free base porphyrins.