54170-75-1Relevant articles and documents
Metallkomplexe mit Tetrapyrrol-Liganden, LVI Synthese, Spektren und Redoxeigenschaften von Europium(III)-Bisporphyrinaten mit identischen und verschiedenen Porphyrin-Liganden
Buchler, Johann W.,Loeffler, Juergen
, p. 531 - 542 (2007/10/02)
The reaction of tris(2,4-pentanedionato)europium(III) with a porphyrin H2(P) in boiling 1,2,4-trichlorobenzene affords a so-called "redox mixture" of europium(III) bisporphyrinates, i.e. porphyrin ?-radicals of the type Eu(P)2 and sandwiches EuH(P)2 in which one of the porphyrin rings is protonated.Thus, from either tetraphenylporphyrin or its dilithium derivative, or octaethylporphyrin, or a mixture of both porphyrins, the corresponding mixtures of double-deckers with two identical or two different porphyrin rings are obtained.The transformation of the redoxmixtures into the pure tetraphenylporphyrin derivatives Eu(TPP)2, EuH(TPP)2, and the salt , the separation of the octaethylporphyrin derivatives Eu(OEP)2 and EuH(OEP)2, and the purification of the "mixed" double-decker Eu(OEP)(TPP) are described.The compounds are characterized by cyclic voltammetry, IR, UV/VIS/NIR, 1H NMR, and mass spectra.The obtained data indicate that the ?-electrons of the two porphyrin rings behave as a common electronic system in which a defect electron is delocalized.However, in the "mixed" double-decker Eu(OEP)(TPP) the defect electron is more concentrated on the OEP ring, i.e. the porphyrin ring which is more easily oxidized.
