Two-Dimensional and Three-Dimensional Coordination Polymers of Hexakis(4-cyanophenyl)[3]radialene: The Role of Stoichiometry and Kinetics

Abstract

Hexakis(4-cyanophenyl)[3]radialene (1) is a hexadentate ligand that has previously been shown to form isomorphous honeycomb two-dimensional (2-D) coordination polymers {[Ag(1)](X)·2(CH3NO2)}n (X = ClO4, 2a; X = PF6, 2b) upon reaction with AgClO4 and AgPF6. Within these coordination polymers, close contacts were observed between the anions and the electron-deficient [3]radialene core. Here the synthesis and characterization of four new coordination polymers of 1 and copper(I), {[Cu2(1)2](X)2·Y(CH3NO2)}n (X = BF4, Y = 20, 4a; X = PF6, Y = 14, 4b) and {[Cu(1)](X)·2(CH3NO2)}n (X = BF4, 5a; X = PF6, 5b), are reported, along with two further examples of the (6,3) network {[Ag(1)](X)·2(CH3NO2)}n (X = BF4, 2c; X = SbF6, 2d), and an 8-fold interpenetrated (10,3)-b net formed from 1 and AgClO4, {[Ag3(1)](ClO4)3·CH3NO2}n (3). Coordination polymers 2a–2d were synthesized using low ratios of ligand to metal, 1:1 to 1:3, whereas other examples described herein (compounds 3, 4, and 5) were obtained via the use of a cons...