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ISSN 1998-9539

Synthesis of Metallated (Cu, Pd) Crown Substituted Tetracyclohexenoporphyrins. Crown-Containing Pd Tetrabenzoporphyrin and its Phosphorescence

Ksenia V. Tikhomirova, Denis E. Chumakov, Andrey V. Khoroshutin,@ and Alexander V. Anisimov


M. V. Lomonosov Moscow State University, 119991 Moscow, Russia


@Corresponding author E-mail:


Palladium and copper tetracyclohexenoporphyrins (cyclohexano rings annelated to pyrrole rings), tri-mesophenylsubstituted and mono-meso-substituted with benzo-15-crown-5 ether moiety (PdPh3[benzo-15-crown-5]TCP
and CuPh3[benzo-15-crown-5]TCP) have been synthesized. Coupling of 1,1-(arylmethylene)bis-4,5,6,7-tetrahydro-
2H-isoindole with the corresponding aldehyde in Lindsey conditions has been used. Two variations of the reagents combinations have been tested. Phenyl substituted dipyrromethane reacted with the mixture of m-formylbenzo-15-crown-5 and benzaldehyde gave the best cyclization results. Separation of the mixture of the scrambled products was greatly enhanced by metallation prior to column chromatography, thus rendering the yields of PdPh3[benzo-15-crown-5]TCP and CuPh3[benzo-15-crown-5]TCP 16% and 18% respectively. An alternative combination of the reagents, i.e. benzo-15-crown-5-substituted isoindole and benzaldehyde, afforded no porphyrin products besides H2Ph4TCP. Oxidation of PdPh3[benzo-15-crown-5]TCP by DDQ yielded the corresponding tetrabenzoporphyrin (PdPh3[benzo-15-crown-5] TBP) in 71%. Phosphorescence spectrum of the latter has been studied.


Keywords: Synthesis, tetracyclohexenoporphyrin, tetrabenzoporphyrin, 15-crown-5, palladium, copper,
dipyrromethanes, phosphorescence.


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