Polymeric bound porphyrines and their precursors, 3. Photoredox properties of combined moieties of porphyrine and phthalocyanine, covalently bound to polystyrene

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].

Dioxa-dithia Macrocycle-bridged Dimeric with Hexakis(alkylthio) Substituents and Network Polymer Phthalocyanines

“…The products 6-9 were purified by successive washing with different solvents, so the insoluble products were obtained in sufficient purity. The intensity of the absorption bands of the end groups is a clear indication of the degree of polymerization in network polymers [7]. The IR spectra of the phthalocyanines 6-9 do not show the presence of C ϵ N groups, so it is not possible to make any evalution on the degree of polymerization by comparing their intensities with the intensity of other groups (e.g.…”

“…A number of polymeric compounds based on repeating units containing phthalocyanine moieties have been synthesized in order to establish their photochemical and electrochemical properties [7][8][9]. Polymeric phthalocyanines are interesting compounds that exhibit qualities as catalysts and semiconductors [10].…”

Phthalocyanine-modified silica gels and their application in the purification of unsymmetrical phthalocyanines

“…Although symmetrical tetra-and octasubstituted phthalocyanines are well known, the synthesis of simple mono-and disubstituted and other unsymmetrical phthalocyanines remains a difficult problem (10-21). For instance, all tetrasubstituted phthalocyanines so far synthesized contain one substituent in each of the benzene rings, and no phthalocyanines such as 1,2,3,4-or 1,2,3,8-tetrasubstituted phthalocyanines have been reported.Successful methods for the synthesis of unsymmetrical phthalocyanines can be divided into three groups according to strategy: (1) the polymer support route (14,16,19,20); (2) the homogeneous mixed condensation route ( 12-14, 2 1); and (3) the subphthalocyanine route (1 1). There are difficulties with all three routes for large-scale preparation of unsymmetrical alkoxy-substituted phthalocyanines.…”

“…Thus, unsymmetrical phthalocyanines are important goals in synthesis. Although symmetrical tetra-and octasubstituted phthalocyanines are well known, the synthesis of simple mono-and disubstituted and other unsymmetrical phthalocyanines remains a difficult problem (10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21). For instance, all tetrasubstituted phthalocyanines so far synthesized contain one substituent in each of the benzene rings, and no phthalocyanines such as 1,2,3,4-or 1,2,3,8-tetrasubstituted phthalocyanines have been reported.…”

“…Successful methods for the synthesis of unsymmetrical phthalocyanines can be divided into three groups according to strategy: (1) the polymer support route (14,16,19,20); (2) the homogeneous mixed condensation route ( 12-14, 2 1); and (3) the subphthalocyanine route (1 1). There are difficulties with all three routes for large-scale preparation of unsymmetrical alkoxy-substituted phthalocyanines.…”