Post‐Synthetic Monovalent Central‐Metal Exchange, Specific I2 Sensing, and Polymerization of a Catalytic [3×3] Grid of [CuII5CuI4L6]⋅(I)2⋅13 H2O

Abstract

From a predesigned grid, [Cu^II₅Cu^I₄L₆]⋅(I)₂⋅13 H₂O (1), in which LH₂ was a pyrazinyl‐triazolyl‐2,6‐substituted pyridine, we successfully synthesized an extended 3D complex, ¹_∞[{Cu^II₅Cu^I₈L₆}{μ‐[Cu^I₃(CN)₆]}₂⋅2 CH₃‐ CN] (2), that displayed unprecedented coexistence of all the five known coordination geometries of copper. Grid 1 displayed monovalent central metal exchange (CME) of Cu^I for Ag^I for the first time, as well as the formation of tri‐iodide in the crystalline state. These systems were investigated for their magnetic properties. Remarkably, grid 1 showed much higher catalytic activity than the Ag‐exchanged product for synthesis of a substituted triazole, 1‐benzyl‐4‐phenyl‐1H‐1,2,3‐triazole.