A Quadruply Bridged Non‐Offset Face‐to‐Face Porphyrin Dimer and Cross‐Shaped Pentameric Porphyrin Tapes Based on 2,7,12,17‐Tetrakis(pinacolatoboryl) NiII Porphyrin

Abstract

Abstract2,7,12,17‐Tetrakis(pinacolatoboryl) NiII porphyrin 5 Ni was synthesized in 75 % yield by Ir‐catalyzed borylation of porphine followed by NiII metalation and has been demonstrated to be a useful synthon, giving 2,7,12,17‐tetraaryated NiII porphyrins 6 a–d, peripherally octaarylated NiII porphyrins 8 a–d, quadruply bridged face‐to‐face non‐offset NiII‐porphyrin dimer 12, and cross‐shaped β‐meso singly linked porphyrin pentamers and nonamers. Oxidation of cross‐shaped β‐meso singly linked porphyrin pentamers 14 Ni and 14 Zn gave fused pentameric tapes 15 Ni and 15 Zn. The structures of 12, 14 Zn, and 15 Ni have been revealed by X‐ray diffraction analysis. Optical separation of 12 has been accomplished, showing a bisignate coupling pattern for exciton‐coupled blue‐shifted Soret band. Pentameric porphyrin tape 15 Zn exhibits a red‐shifted absorption band at 1156 nm and seven reversible redox waves.