Abstract
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: C48H48S12Cl6Bi2, triclinic, P1, a = 7.7535(3) A, b = 13.8362(5) A, c = 14.0188(5) A, α = 107.763(1)°, β = 98.730(1)°, γ = 97.020(1)°, V = 1392.76(9) A3, and Z = 1] features a composite one-dimensional BiCl3 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 lin...
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