A new synthetic method of bridged metallotetraphenylporphyrin polymers

For the first timer a new method which depends on the pressure produced by solvent itself, was adopted to synthesize a series of bridged metallotetrap henylporphyrin polymers-[M(TPP)L](n)(M = Fe (III), Co(II), Mn(III), Ni(II) and Cu(II); L = pyrazine, imidazole, bipyridine), These compounds were char acterized by the methods of UV, photovoltaics, and IR spectroscopy, In soli d UV reflecting and photovoltaics spectra, the Soret band of the polymer is dramatically blue-shifted. For the monomer - Co(TPP) (pyz)(2) of unidentat e pyrazine, the IR spectra showed a strong absorption at 1 598 cm(-1), whil e only an extremely weak absorption at near 1 600 cm(-1) for polymer [Co(TP P)(pyz)](n). The strong absorption of the monomer at 3 482, 3 423, 2 921, 2 854, 1 004, 792 and 611 cm(-1) almost disappeared in the polymer, indicati ng an increase in the symmetry of the polymer compared with the monomer; wh ile the bands at 1 644, 1 353 and 1 070 cm(-1) belonging to the monomer shi fted 13, 25 and 15 cm(-1) towards higher field in polymer, respectively. Th e behavior is concerned with a high proportion of symmetrically bridged pyr azine, which testified that the order of the whole molecule and the interac tion between porphyrin macrocycles were intensified after the metalloporphy rin linked with the axial ligand, All of these proved that we have synthesi zed the target products through this new method successfully. In addition, it was observed that the time for which the reactants polymerized varied co nsiderably, depending on both the metal, was in the order of Co(II)<(Fe(III )<Ni(II)<Cu(I)< Mn(III), and the ligand, in the order of bipyridine<pyrazin e<imidazole.