Synthesis of Box-shaped Pentaporphyrin with Cobalt(II) Porphyrin in the Center; Reversible O2 Binding in the Box

Abstract

Abstract Aiming at construction of robust molecular architectures having an active center surrounded by stable walls, a box-shaped cobalt(II)–rhodium(III) pentaporphyrin [Co(tpyp)][Rh(tpp)Cl]4 (2) (tpyp = 5,10,15,20-tetrapyridylporphyrinato dianion, tpp = 5,10,15,20-tetraphenylporphyrinato dianion) was newly synthesized via coordination bonds. The cobalt(II) center of the complex 2 reacts reversibly with O2 to give a corresponding dioxygen complex of [Co(tpyp)(py)(O2)][Rh(tpp)Cl]4 (2-(py)(O2)) at low temperatures in dichloromethane-containing pyridine.