Three-Dimensional Photoluminescent Frameworks Constructed from Size-Tunable CuI Clusters

Reported here are three 3-D copper iodide frameworks, (Cu4I4)(DABCO)2(solvent)x (1), (Cu6I6)(Cu8I8)(DABCO)5(imidazole) (2), and (Cu2I2)1/2(Cu5I5)(DABCO)2 (3), constructed with DABCO ligands (DABCO = 1, 4-diazabicyclo-[2.2.2]-octane) and various neutral CuI clusters. 1, 2, and 3 display an interpenetrating diamond-type net, a 5-connected interpenetrating net, and a (4,6)-connected net, respectively. The variations in Cu+ coordination numbers (2, 3, and 4), cluster types, and framework topologies are achieved by tuning reactant ratios and by employing different mixed solvents. Compound 3 displays chiral symmetry, while compound 2 shows photoluminescence at 298 K.