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)center dot 7DMA center dot 10H(2)O (1) and [NH2(CH3)(2)][In-3(OH)(2)(H2O)(2)(ina)(8)(Cu4I4)(2)]center dot 5DMA center dot 8H(2)O (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 [In-3(OH)(2)(CO2)(8)](-) trimer and a cubane-like Cu4I4 cluster. Especially, 1 displays a reversible I-2 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.