CuI Cluster-Based Organic Frameworks with Unusual 4- and 5-Connected Topologies

Reported here are two three-dimensional CuI cluster-based organic frameworks, (Cu4I4)2(Cu6I6)(DABCO)6 (1) and (Cu4I3)2(CN)2(DABCO)3 (2) (DABCO = 1,4-diazabicyclo[2.2.2]octane) constructed from mixed CuI clusters and mixed linear ligands, respectively. Compound 1 displays an unprecedented 4-connected network based on Cu4I4 and Cu6I6 clusters, respectively, as tetrahedral and pseudosquare planar 4-connected nodes, while 2 displays a novel 5-connected BN-type network composed of 5-connected cationic Cu4I3+ clusters linked by mixed cyanide anion CN− and DABCO ligands. The CN− in 2 derives from the solvent CH3CN and adopts a rare μ4-bridging mode. 1 shows chiral symmetry and photoluminescence at 298 K. The mixed strategies prove to be a useful fool to enrich the synthetic chemistry and structural diversity of cluster organic frameworks.