meso ‐5‐Bromo‐10,15,20‐tri( p ‐tolyl)‐21‐thiaporphyrin as a Precursor for the Synthesis of Novel Compounds

The synthesis of eight novel compounds with meso ‐5‐bromo‐10,15,20‐tri( p ‐tolyl)‐21‐thiaporphyrin as a key synthon under mild Pd‐coupling conditions is reported. The title compound was prepared easily by treating the readily available 10,15,20‐tri( p ‐tolyl)‐21‐thiaporphyrin with N ‐bromosuccinimide at room temperature for 10 min. The use of the title compound was demonstrated by synthesizing 21‐thiaporphyrin‐based complex systems such as ethyne‐bridged N 3 S‐N 3 S dyad, phenylethyne‐bridged N 3 S‐N 3 O dyad, N 3 S‐N 2 S 2 dyad, meso ‐ meso ‐linked ZnN 4 ‐N 3 S dyad and ZnN 4 ‐N 3 S‐ZnN 4 triad under mild Pd‐mediated coupling conditions. The steady‐state fluorescence studies indicated a possibility of an efficient energy transfer between the two porphyrin subunits in the dyads and triad. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)