No abstract

Copolymers containing covalently bound phthalocyanine moieties (4) or tetraphenylporphyrine moieties (5) were prepared by the reaction of partially chloromethylated polystyrene (3) with the low molecular substituted phthalocyanine 1 b and tetraphenylporphyrine 2b, respectively. Combined binding of moieties of 1 b and 2 b yielded polymer 6. The photoredox behavior of 1,2,4,5 and 6 was investigated under irradiation with visible light in the presence of a donor and an acceptor. Mixtures of sensitizers (1 + 2 and 4 + 5) resulted in reduced photocatalytic properties. Only in the case of 6, due to reduced intermolecular interactions, higher yields of photochemical reaction products were obtained. (So, , (NH)), 760/702 (Ar-H) and 606/507/528 cm -I ((C-C) of phenyl). UV/VIS (DMSO): L/nm (&/(1. mol-' -c m -' ) = 614, 565,438 (125000). Poly(styrene-co-chloromethyfstyrene) (3): 20,s g (0,2 mol) of freshly distilled styrene and 1,5 g (0,l mol) of freshly distilled 4chloromethylstyrene were dissolved in 20 ml of toluene. The solution was heated in a sealed ampoule with 2 mol-% AIBN (recrystallized from ethanol) for 3 h at 323 K. The copolymer was precipitated in methanol, reprecipitated from toluene/ methanol and dried i. vac. at 323 K. Yield: 5,3 g. The composition of the copolymer was determined by C1-analysis and was found to be 0 3 5 mmol C1 per g polymer (rnol ratio of styrene monomeric units to chloromethylstyrene monomeric units = 16 t o 1). Intrinsic viscosity [q] (in methanol at 307 K) = 12,8 ml/g, corresponding to M,, = 17000. M , was found to be 14000 by vapour pressure osmometry in toluene. IR (KBr): 1263 cm-l (v(CH2-Cl)) and additional absorptions of polystyrene.Polymer 4.): 0,s g (0,s mmol) of lb and 27 mg (0,s mmol) of sodium methoxide were dissolved in 50 ml of DMA. A solution of 0,9 g (0,5 mmol) of 3 in 50 ml of DMA was added *) Poly[styrene-co-4-cNoromethylstyrene-co-zinc-~[4-[9,16,23-tetrakis(4-hydroxyphenoxy)-29H,31 H-phthalocyanine-2-yloxy]phenoxymethyl)styrene].

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.').