A New Synthetic Method of Bridged Metallotetraphenylporphyrin Polymers
LI Xiang-Qing, WANG Li-Ping, DING Hong, MENG He, YU Lian-Xiang, GUO Jing-Fu, WANG Xing-Qiao, HE Shu-Hua
1999, 20(9):
1338-1342.
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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.
