Positively or negatively charged as well as uncharged water-soluble polymers 2a-d, 6a-c, 7a-e and positively charged crosslinked polymers 3a, b containing covalently bonded moieties of the substituted zinc tetraphenylporphyrin 1 a were prepared. In addition, positively charged polymers 4a-c with covalently bonded viologen, and 5 with covalently bonded 1 a and viologen at one and the same polymer chain were obtained. The triplet lifetimes in water of different l abonded linear polymers 2a-d, 6a-c, and 7a-e are not influenced by the kind of polymer environment. The photoredox activities in water of the polymers containing moieties of 1 a in the presence of methylviologen and 2-mercaptoethanol under irradiation with visible light are higher as compared with low-molecular-weight, positively or negatively charged porphyrins 1 b, c. The influence of the amount of polymer-bonded porphyrin and the molecular weight of a polymer on the photoredox activity is exemplarily described. Polymers 4a-c with viologen moieties as acceptor are more efficient than the low-moleular-weight methylviologen. The highest photoredox activities were observed with polymer 5 containing moieties of 1 a and viologen. In the presence of the enzyme hydrogenase formation of hydrogen occurs. 0 1991, Hiithig & Wepf Verlag, Basel CCC 0025-1 16X/91/$03.00

Water-soluble polymers 6 -17 containing covalently bound moieties of porphyrin derivatives were prepared by reaction of poly(methacry1ic acid) (4) and poly(N-vinylpyrrolidone-co-methacrylic acid) (5) with the low-molecular-weight substituted tetraphenylporphyrin 1 b, phthalocyanines 2 b and 2d and naphthocyanine 3c. Besides binding of one porphyrin derivative, also combined binding of two or three different porphyrin derivatives to the polymers could be achieved. The resulting polymers are negatively charged (polymers 6 -11) or uncharged (polymers 12 -17).

Positively charged polymers 6 -13 containing covalently bound moieties of tetraphenylporphyrin (l), phthalocyanine 2 and naphthocyanine 3 were obtained by reaction of poly(ch1oromethylstyrene) with low-molecular weight substituted porphyrins ( l b , 2b, 2d, 3c) in the presence of triethylamine. The water-soluble polymers contain moieties of one or of two or three different porphyrin derivatives. a) Part 6: cf.').