Ligand-Bridged Heterobimetallic Polymers: Silver(I)−Benzothiadiazole−Nickel Porphyrin Cation−Benzothiadiazole Arrays

Abstract

Stable crystals of (NiOETPP(BTD)2+)(Ag+)(ClO4)2·2CH2Cl2 were obtained from the oxidation of NiOETPP with AgClO4 in CH2Cl2 followed by addition of BTD. (OETPP = 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetraphenylporphyrin; BTD = 2,1,3-benzothiadiazole). An X-ray structure reveals that the complex is a bimetallic polymeric aggregate composed of [−Ag+−BTD−NiP+−BTD−] subunits in which the BTDs act as bidentate ligands that bind to the Ni and Ag ions via their their two nitrogens. As in the parent NiOETPP, the ligated oxidized porphyrin adopts a severely distorted saddle conformation. The saddle distortion and peripheral substituents form superstructural trenches that control the orientations of the two BTD axial ligands which are forced into a nearly orthogonal configuration along the axes defined by opposite porphyrin nitrogens.