Solid-state structural transformations in metal organic-inorganic hybrids constructed from terbium(III) complexes and iodocuprate clusters

摘要: Using precursors of the type [Tb(DMSO)8]I3 (a) and [Tb(DMF)8]I3 (b), syntheses two new heterometal organic–inorganic hybrid complexes based on discrete iodocuprate clusters [Tb(DMSO)8][Cu2I5] (1) [Tb(DMF)8][CuI3][I] (2), respectively, are reported. Though stable in air for few days, colorless complex 1 slowly turns into a purple-colored mixture over course several days. Two complexes, namely [Tb(DMSO)8][CuI3][I] (3) [Tb(DMSO)8](I)2(I3) (4), were isolated from this characterized structurally, I3− anion latter being responsible purple color mixture. In comparison, 2 is quite deliquescent but undergoes solid state structural transformation confined environment paratone to afford 2D honeycomb-like microporous structure containing mixed-valent copper atoms [Tb(DMF)6(H2O)3][CuII2CuI7I14]2∞ (5), bifurcate H-bonding between water ligands terbium iodides Cu–I cluster playing pivotal role evolution its structure. Single crystal X-ray structures reported all complexes. Thermal luminescent properties 2, which obtained exclusively pure form, described. Compared precursor iodide high energy transitions excitation spectra quenched by auto-ionization carriers material.