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A stable 3d–4fheterometallic cluster, namely, {Dy4Ni5L10(NO3)4(CO3)4(CH3OH)2}·CH3CN (Dy4Ni5, HL = 8-hydroxyquinoline), has been solvothermally synthesized and structurally characterized. The compound exhibits an interesting structure in which a tetrahedron based on 4fions interpenetrates with a square pyramid based on 3dions. Besides, a unique intermolecular interaction was found in Dy4Ni5, giving rise to its high stability not only when it is in the solid state but also when it dissolves in organic solvents. In addition, the magnetic behavior of solid Dy4Ni5and the magneto-optical activity of the Dy4Ni5solution were also studied.

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. 1shows 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 Cu2I2cluster. Comparably, 2displays a 3D negative network with irregular hexagonal channels constructed from a [In3(OH)2(CO2)8]−trimer and a cubane-like Cu4I4cluster. Especially, 1displays a reversible I2adsorption/release performance with high adsorption capacity, whose mechanism has been disclosed by theoretical simulation. Also, the green/red emission of 2stems from iodocuprate centers with quenched indium-centered emission.

A rare 3D Indium-containing polyoxoniobate framework {H9[Cu(en)2(H2O)2][Cu(en)2]12[In(en)]5[Nb23–O65(OH)3(H2O)2]{Nb24O67(OH)2(H2O)3]2}·68H2O(1), based on the In-containing polyoxoniobate cluster, {[In(en)]5[Nb23O65(OH)3(H2O)2][Nb24O67(OH)2(H2O)3]2}35–({In5Nb71}) and [Cu(en)2]2+linkers has been successfully synthesized. The nest-like cluster {In5Nb71} is constructed from one brand-new V-shaped {Nb23O70}, two triangle-shaped {Nb24O72} and five [In(en)]3+. The [In(en)] fragments link {Nb24O72} and {Nb23O70} units into unique {In5Nb71}nhelical pillars. The copper-amine complexes connect the {In5Nb71}nhelical pillars into a three-dimensional (3D) inorganic–organic hybrid In–Cu-containing framework. This material also exhibits good ionic conductivity and vapor adsorption capacity properties.