Face-to-Face Gold Porphyrins

The interaction of square-planar metal complexes through space is of fundamental interest and relevant for the potential cooperative catalysis of two metal complex sites. In order to elucidate gold/gold, gold/porphyrin, and porphyrin/porphyrin interactions in the formal oxidation states +III and +II (after reduction) and in the excited triplet state after light excitation, a Pacman bis(gold(III)) complex [Au₂(DPD)][PF₆]₂ with square-planar face-to-face gold(porphyrin) moieties has been prepared and characterized. Absorption and luminescence spectroscopy, cyclic voltammetry, and EPR spectroscopy on [Au₂(DPD)]^<i>n</i>+ and a mononuclear reference are complemented by DFT and TDDFT calculations.