A Semiconductive coordination network based on 2,3,6,7,10,11- hexakis(methylthio)triphenylene and BiCl₃

The reaction of 2,3,6,7,10,11-hexakis(methylthio)triphenylene (1) with BiCl₃ in benzene forms near-quantitatively the crystalline composite 1·BiCl₃, which is an air stable semiconductor with an electronic band gap of 2.0 eV (diffuse reflectance data). The crystal structure of 1·BiCl₃ [crystal data: C₄₈H₄₈S ₁₂Cl₆Bi₂, triclinic, P1, a = 7.7535(3) Å, b = 13.8362(5) Å, c = 14.0188(5) Å, α = 107.763(1)°, β = 98.730(1)°, γ = 97.020(1)°, V = 1392.76(9) ų, and Z = 1] features a composite one-dimensional BiCl ₃ framework in which the Bi(III) center is chelated to the organic ligand. The chelation bonds facilitate the ligand-metal center interaction and generate substantial charge transfer phenomena. The ease of crystallization is ascribed to the relatively weak Bi(III)-Cl bonds that serve to connect the organic ligands and the similar crystalline packing motifs of the reactant (1) and the product (1·BiCl₃). The synthesis of compound 1·BiCl₃ indicates that semiconductive networks can be effectively accessed by linking electroactive organic ligands through intervening metal halide moieties. Compound 1·BiCl₃ can also be made in a solvent-free solid state reaction. © 2005 American Chemical Society.