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

Reported here are two three-dimensional CuI cluster-based organic frameworks, (Cu 4 I 4 ) 2 (Cu 6 I 6 )(DABCO) 6 ( 1 ) and (Cu 4 I 3 ) 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 Cu 4 I 4 and Cu 6 I 6 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 Cu 4 I 3 + clusters linked by mixed cyanide anion CN − and DABCO ligands. The CN − in 2 derives from the solvent CH 3 CN and adopts a rare μ 4 -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.