SYNTHESES OF HOMOPOLYMER AND WATER-SOLUBLE POLYMERS CONTAINING TETRAPHENYLPORPHINATOMANGANESE(III) COMPLEX, AND LIGAND SUBSTITUTION-REACTION FOR ANIONIC LIGAND

A vinyl monomer containing the pendant tetraphenylporphyrin (TPP) grou p, 4-vinyltetraphenylporphyrin (VTPP), was synthesized. A homopolymer (PVTPP) which is insoluble in water, and three water-soluble polymers were obtained by radical polymerization. The water-soluble polymers ar e two anionic polymers (PVPTSPP and PVTPP-StSO3) and a cationic polyme r (PVTPP-VPyM). PVPTSPP has sulfonic acid groups in a TPP group and ve ry high charge density. PVTPP-StSO3 was obtained by copolymerization o f VTPP and sodium 4-styrenesulfonate. PVTPP-VPYM was obtained by quart ernarization of a copolymer of VTPP and 4-vinylpyridine. Polymeric man ganese(III) complexes (PMnVTPP, PMnVPTSPP, PMnVTPP-StSO3, and PMnVTPP- VPyM) were prepared from the polymers and manganese acetate. The aceta te ligand in PMnVTPP can be easily substituted by another ligand such as Cl-, AcO-, OH-, and SCN-. The substitution reaction occurs in the i nterface between water and chloroform. The sulfonated homopolymer, PMn VPTSPP, cannot incorporate with anionic ligands because of the strong electrostatic repulsion. In the anionic copolymer, PMnVTPP-StSO3, the ligand substitution reaction with SCN ligand needs activation energy o f 53 kJ/mol. In the cationic polymer complex, PMnVTPP-VPyM, the OH lig and can be easily substituted with the SCN ligand and the equilibrium constant of the reaction was estimated at 1.38 X 10(-3). (C) 1994 John Wiley & Sons Inc.