Multiple Roles of 1,4-Diazabicyclo[2.2.2]octane in the Solvothermal Synthesis of Iodobismuthates

[Image: see text] Hybrid bismuth-containing halides are emerging as alternative candidates to lead-containing perovskites for light-harvesting applications, as Bi(3)(+) is isoelectronic with Pb(2)(+) and the presence of an active lone pair of electrons is expected to result in outstanding charge-carrier transport properties. Here, we report a family of one binary and three ternary iodobismuthates containing 1,4-diazabicyclo[2.2.2]octane (DABCO). These materials have been prepared solvothermally and their crystal structures, thermal stability, and optical properties determined. Reactions carried out in the presence of bismuth iodide and DABCO produced (C(6)H(12)N(2))BiI(3) (1), which consists of hybrid ribbons in which pairs of edge-sharing bismuth octahedra are linked by DABCO ligands. Short I···I contacts give rise to a three-dimensional network. Similar reactions in the presence of copper iodide produced (C(8)H(17)N(2))(2)Bi(2)Cu(2)I(10)(2) and [(C(6)H(13)N(2))(2)BiCu(2)I(7)](C(2)H(5)OH) (3) in which either ethylated DABCO cations (EtDABCO)(+) or monoprotonated DABCO cations (DABCOH)(+) are coordinated to copper in discrete tetranuclear and trinuclear clusters, respectively. In the presence of potassium iodide, a unique three-dimensional framework, (C(6)H(14)N(2))[(C(6)H(12)N(2))KBiI(6)] (4), was formed, which contains one-dimensional hexagonal channels approximately 6 Å in diameter. The optical band gaps of these materials, which are semiconductors, range between 1.82 and 2.27 eV, with the lowest values found for the copper-containing discrete clusters. Preliminary results on the preparation of thin films are presented.