Synthesis, characterization and electrochemistry of bismuth porphyrins. X-ray crystal structure of (OEP)Bi(SO3CF3)

The metalation of several free base porphyrins by the bismuth salts BiO(NO3 )(3) and Bi(SO3CF3)(3) in DMF or pyridine is described. The resulting stabl e Bi(LII) porphyrin complexes are characterized by electrochemistry, H-1 NM R and UV-vis spectroscopy. The structure of (OEP)Bi(SO3CF3) was also determ ined by single-crystal X-ray diffraction and shows that (OEP)Bi(SO3CF3) exi sts as a dimer which is stabilized by electrostatic interactions in which t he two [(OEP)Bi](+) cations are linked via oxygen atoms of two symmetricall y related SO3CF3- anions, leading to a heptacoordinated bismuth center. Ele ctrochemical oxidation of (OEP)Bi(SO3CF3) and (TpTP)Bi(SO3CF3) shows that o nly the porphyrin macrocycles are oxidized. Copyright (C) 2000 John Wiley & Sons, Ltd.