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

The Electronic Structure of Tetrabromotetraphenylporphyrin and Its Metalloporphyrins [M = Cu(Ⅱ), Co(Ⅱ), Ni(Ⅱ), Zn(Ⅱ)] and the Crystal Structure of Ni(Ⅱ)TPPBr_4

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_4[M=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,空间群为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.

7, 8, 17, 18-tetrabromo-5, 10, 15, 20-tetraphenylporphyrin (H2TPPBr4) and its metalloporphyrins [MTPPBr4 M = Cu(Ⅱ), Co(Ⅱ), Ni(Ⅱ), Zn(Ⅱ)] were synthesized. Their UV-Vis spectra and cyclic volammetry were determined. The relative energy of frontier orbital of metalloporphyrins, which explained the characters of UV-Vis spectra and electrochemistry, were calculated according to four orbital parameters. The crystal structure of NiTPPBr4 was determined by a CAD4 diffractometer. Crystllographic parameters were as follows: Monoclinic, space group C2 / c with a = 2.6077(7)nm, b= 1.0414(4)nm, c= 1.9312(3) nm; β= 137.1(7)°, Z=4, F(000) = 2048, final R= 0.067. This structure directly verified that electrophilic bromination occured regiospecifically at the antipodal pyrrolenic ring of free base porphyrins.