Heterometallic Organic Frameworks Built from Trinuclear Indium and Cuprous Halide Clusters: Ligand-Oriented Assemblies and Iodine Adsorption Behavior.

Two novel heterometallic organic frameworks built from trinuclear indium and cuprous halide clusters, [(In3O)2(Cu2I2)3(ina)12(H2O)6](NO3)2·7DMA·10H2O (1) and [NH2(CH3)2][In3(OH)2(H2O)2(ina)8(Cu4I4)2]·5DMA·8H2O (2), where Hina = isonicotinic acid, have been successfully constructed with the orientation of the ina ligand. 1 shows a fascinating highly porous honeycomb-like 3D cationic framework with a trigonal-bipyramid-type cage based on a planar [In3O(CO2)6]+ trimer and a rhombohedral Cu2I2 cluster. Comparably, 2 displays a 3D negative network with irregular hexagonal channels constructed from a [In3(OH)2(CO2)8]- trimer and a cubane-like Cu4I4 cluster. Especially, 1 displays a reversible I2 adsorption/release performance with high adsorption capacity, whose mechanism has been disclosed by theoretical simulation. Also, the green/red emission of 2 stems from iodocuprate centers with quenched indium-centered emission.