Abstract

Four novel rhenium cluster complexes with the general formula trans-[Re₆Q₈(ppy)₄X₂]·n(ppy) (Q = S, Se; X = Cl, Br; ppy = 4-phenylpyridine) are obtained by the interaction of salts Cs_n[Re₆Q₈X₆]·2H₂O (Q = S, n = 4; Q = Se, n = 3; X = Cl or Br) with a 4-phenylpyridine melt. The single-crystal XRD study shows that the structures of these compounds contain molecular fragments trans-[Re₆Q₈(ppy)₄X₂] packed together with 4-phenylpyridine solvate molecules and connected with these molecules by weak interactions, including hydrogen bonds and π-stacking of aromatic rings. It is shown that different halide and chalcogenide ligands of the cluster complex form different types of packing. The obtained compounds are insoluble in water and in organic solvents. The crystal samples are luminescent in the red region with emission peaks at 708-718 nm, quantum yields of 0.01-0.03, and emission lifetimes of ~ 4 μs. The electronic structure of these compounds contains ligand-centered LUMO–LUMO+3 levels localized between metal-centered HOMO and LUMO+4 levels.

中文翻译：

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以 4-苯基吡啶分子为末端配体的分子铼簇复合物的合成、结构和物理化学性质

摘要

四种具有通式反式- [Re ₆ Q ₈ (ppy) ₄ X ₂ ]· n (ppy) ( Q  = S, Se; X  = Cl, Br; ppy = 4-苯基吡啶)的新型铼簇配合物可通过以下方式获得盐 Cs _n [Re ₆ Q ₈ X ₆ ]·2H ₂ O（Q  = S，n  = 4；Q  = Se，n  = 3；X  = Cl 或 Br）与 4-苯基吡啶熔体的相互作用。单晶XRD研究表明这些化合物的结构含有分子碎片trans- [Re ₆ Q ₈ (ppy) ₄ X ₂ ] 与 4-苯基吡啶溶剂化物分子堆积在一起，并通过弱相互作用与这些分子连接，包括氢键和芳环的 π 堆积。结果表明，簇络合物的不同卤化物和硫属化物配体形成不同类型的堆积。所得化合物不溶于水和有机溶剂。晶体样品在红色区域发光，发射峰在 708-718 nm，量子产率为 0.01-0.03，发射寿命约为 4 μs。这些化合物的电子结构包含位于以金属为中心的 HOMO 和 LUMO+4 能级之间的以配体为中心的 LUMO-LUMO+3 能级。