Structure and photophysical and electrochemical properties of a copper porphyrin complex with a three‐dimensional framework

摘要

Porphyrins and metalloporphyrins can generally show attractive structural motifs and interesting properties. A new copper porphyrin, namely poly[[μ‐chlorido‐[μ 5 ‐5,10,15,20‐tetrakis(pyridin‐4‐yl)‐21 H ,23 H ‐porphine]tricopper(I)] [aquadichloridocopper(II)]], {[Cu 3 (C 40 H 24 N 8 )Cl][CuCl 2 (H 2 O)]} n ( 1 ), was synthesized by the self‐assembly of copper chloride with 5,10,15,20‐tetrakis(pyridin‐4‐yl)‐21 H ,23 H ‐porphine under solvothermal conditions. The structure of this copper porphyrin was characterized by single‐crystal X‐ray crystallography and elemental analysis. The porphyrin macrocycle shows a distorted saddle geometry, with the four pyrrole rings slightly distorted in an alternating mode either upwards or downwards. The copper ions show three‐coordinated triangular and four‐coordinated square‐planar geometries. Every copper–porphyrin unit connects to 12 others via four μ 4 ‐bridging Cu 2 Cl moieties to complete the three‐dimensional framework of compound 1 , with isolated CuCl 2 (H 2 O) units located in the voids. This copper porphyrin displays a red photoluminescence. Electrochemical measurements showed that compound 1 has two redox waves ( E 1/2 ?= ?160 and 91?mV).