Abstract
Meso-tetrakis (4-bromo-2-thiophene) and (5-bromo-2-thiophene) porphyrins were synthesized in 18% yield from freshly distilled pyrrole and the corresponding aldehydes in refluxing propionic acid. Reaction of both porphyrins with either Zn(OAc)(2)center dot 2H(2)O Or Ag(OAc) afforded the corresponding metal complexes in 20% yield. The free bases and metal complexes were characterized by IR, NMR, EPR, MS and XPS. The crystal structure of 5,10,15.20(4-bromo-2-thiophene)porphyrinato Zn(II) was determined by X-ray diffraction and shows a 'zigzag-like' packing pattern due to S S intermolecular interaction. Structural features of these molecules are discussed by DFT quantum chemical calculations. (C) 2008 Elsevier B.V. All rights reserved.