密闭高压法合成桥连金属四苯基卟啉多聚物

采用密闭高压法合成出一系列桥连金属四苯基卟啉多聚物M(TPP)L]_nM＝Fe(Ⅲ),Co(Ⅱ),Mn(Ⅱ),Cu(Ⅱ),Ni(Ⅱ);L＝吡嗪,咪唑,联吡啶].通过固体紫外反射、光电压和红外等方法予以表征.在固体紫外反射和光电压光谱中,金属卟啉聚合物的Soret带均发生了显著蓝移.在红外光谱中,单体Co(TPP)(pyz)₂在1598cm^-1处显示一个强吸收,而聚合物Co(TPP)(pyz)]_n在1600cm^-1附近仅有极弱的吸收,单体在3482,3423,2921,2854,1004,792和611cm^-1处出现的强吸收在聚合物中接近消失,说明此聚合物与单体相比对称性增加,而单体在1644,1353和1070cm^-1处的吸收分别向高场方向位移13,25和15cm^-1.实验中还发现,对于不同中心金属离子,反应完成的时间不同,时间由短到长的顺序为:Co(Ⅱ)＞Fe(Ⅲ)＞Ni(Ⅱ)＞Cu(Ⅱ)＞Mn(Ⅲ);不同桥连配体反应完成的时间由短到长顺序是联吡啶＞吡嗪＞咪唑.

A New Synthetic Method of Bridged Metallotetraphenylporphyrin Polymers

For the first time, a new method which depends on the pressure produced by solvent itself, was adopted to synthesize a series of bridged metallotetraphenylporphyrin polymers-M(TPP)L]_n(M= Fe(Ⅲ), Co(Ⅱ), Mn(Ⅲ), Ni(Ⅱ) and Cu(Ⅱ); L=pyrazine, imidazole, bipyridine).These compounds were characterized by the methods of UV, photovoltaics, and IRspectroscopy.In solid UVreflecting and photovoltaics spectra, the Soret band of the polymer is dramatically blue-shifted.For the monomer -Co(TPP)(pyz)₂of unidentate pyrazine, the IRspectra showed a strong absorption at 1598 cm^-1, while only an extremely weak absorption at near 1600 cm^-1for polymer Co(TPP) (pyz)]_n.The strong absorption of the monomer at 3482, 3423.2921, 2854, 1004, 792 and 611 cm^-1almost disappeared in the polymer, indicating an increase in the symmetry of the polymer compared with the monomer; while the bands at 1644, 1353 and 1070 cm^-1belonging to the monomer shifted 13, 25 and 15 cm^-1towards higher field in polymer, respectively.The behavior is concerned with a high proportion of symmetrically bridged pyrazine, which testified that the order of the whole molecule and the interaction between porphyrin macrocycles wereintensified after the metalloporphyrin linked with the axial ligand.All of these proved that we have synthesized the target products through this new method successfully.In addition,it was observed that the time for which the reactants polymerized varied considerably, depending on both the metal, was in the order of Co (Ⅱ)＜Fe (Ⅲ)＜Ni (Ⅱ)＜Cu (Ⅱ)＜Mn(Ⅲ), and the ligand, in the order of bipyridine＜pyrazine＜imidazole.