A new approach to the synthesis of porphyrin-fullerene dyads.
A new synthetic approach to porphyrin-fullerene dyads utilizing tetraphenylporphyrin (TPP) and three novel reactions (vicarious nucleophilic substitution, metathesis, and [4+2]-cycloaddition to fullerene) is described. 5-(4-Nitrophenyl)-10,15,20-triphenylporphyrin zinc complex reacts with the carbanion of chloromethyl para-tolyl sulphone (which bears a leaving group Cl at the carbanionic center), affording the nucleophilic substitution of hydrogen product containing a CH2SO2Tol group. The product obtained when alkylated with an alkyl halide (bearing an acetylenic function in the terminal position), followed by the cross-enyne metathesis reaction (with the use of an efficient ruthenium catalyst), resulted in the formation of a TPP-diene building block. Its Diels-Alder reaction with C60-fullerene led to the title dyad--a new artificial photosynthetic model. This method opens up the possibility for synthesis of dyads with variable distances between chromophores, depending on the type of the alkyl halides used.
Ostrowski
Stanisław
S
Institute of Chemistry, University of Podlasie, ul. 3 Maja 54, Siedlce, Poland. stan@ap.siedlce.pl
Mikus
Agnieszka
A
D001952:Bridged-Ring Compounds / Q000737:chemistry*; D015394:Molecular Structure; D011166:Porphyrins / Q000138:chemical synthesis* / Q000737:chemistry*; D015032:Zinc / Q000737:chemistry
D001952:Bridged-Ring Compounds; D011166:Porphyrins; C409084:tetraphenylporphyrin; D015032:Zinc