Universität Bielefeld, Lehrstuhl für Anorganische Chemie und Strukturchemie, Universitätsstraße 25, 33615 Bielefeld, Germany.
Dalton Trans. 2013 Nov 28;42(44):15785-95. doi: 10.1039/c3dt52030g.
Alkali metal salts of a novel Janus scorpionate ligand (Tr(Me)) with hard and soft donor sites (N, S) were synthesized by the reaction of 3-mercapto-4-methyl-1,2,4-triazole (L) with NaBH4 and KBH4, respectively, via Trofimenko's protocol. The resulting compounds were the sodium and potassium complexes [Na(Tr(Me))] (1), [K(Tr(Me))] (2) and the mixed ion compound [KNa(Tr(Me))] (3). [K(Tr(Me))] (2) was reacted with bismuth(III) chloride to afford the complexes [Bi(Tr(Me))(Cl)(μ-Cl)2]2 (5) and [Bi(Tr(Me))(Cl)2(μ-Cl)]n (6). Compound 5 was formed when 2 was applied to BiCl3 in a molar ratio 2:1, while 6 was achieved when a ratio of 1:1 was used. The reaction of 3-mercapto-4-methyl-1,2,4-triazole (L) with BiCl3 led to the formation of the complex [Bi(L)4(Cl)2]Cl (7). The products were characterized by NMR and IR spectroscopy, elemental analyses and mass spectrometry. Solid state structures were determined by X-ray diffraction of single crystals of 1, 3, 3a, 5, 6 and 7. The alkali metal scorpionates 1-3 are coordination polymers with alternating orientation of the ligands. They dissociate in solution as observed in NMR measurements. Negative mode ESI-MS data also indicate the presence of monomers. The bismuth complex 5 is dimeric and 6 is polymeric, and both are bridged via chloro ligands. The three bismuth complexes 5, 6 and 7 have highly distorted octahedral coordination geometries. The influence of the stereochemically active lone pair was found to be most pronounced in the dimeric complex 5. The ligand Tr(Me) and all bismuth complexes were also screened for their photo-luminescence activity. Whereas solutions of Tr(Me) exhibit no luminescence, 7 is only emissive at 77 K, and 5 is emissive both at r.t. and 77 K.
通过 Trofimenko 反应，分别用 NaBH4 和 KBH4 与 3-巯基-4-甲基-1,2,4-三唑（L）反应，合成了具有软硬给体（N，S）位点的新型 Janus 星状配体(Tr(Me))的碱金属盐。所得化合物分别为钠盐和钾盐Na(Tr(Me))、K(Tr(Me))和混合离子化合物KNa(Tr(Me))。K(Tr(Me))与三氯化铋反应得到配合物[Bi(Tr(Me))(Cl)(μ-Cl)2]2(5)和[Bi(Tr(Me))(Cl)2(μ-Cl)]n(6)。当 2 与 BiCl3 的摩尔比为 2:1 时，形成 5，当使用 1:1 的比例时，形成 6。3-巯基-4-甲基-1,2,4-三唑（L）与 BiCl3 反应生成配合物[Bi(L)4(Cl)2]Cl(7)。通过对 1、3、3a、5、6 和 7 的单晶进行 X 射线衍射，确定了产物的结构。产物通过 NMR 和 IR 光谱、元素分析和质谱进行了表征。碱金属星状化合物 1-3 是具有交替配体取向的配位聚合物。它们在溶液中会解离，这在 NMR 测量中可以观察到。负离子 ESI-MS 数据也表明存在单体。二聚体 5 和聚合物 6 都是通过氯桥连接的，5 是二聚体，6 是聚合物。这三个铋配合物 5、6 和 7 具有高度扭曲的八面体配位几何形状。发现立体化学活性孤对电子的影响在二聚体 5 中最为显著。还对配体 Tr(Me)和所有铋配合物的光致发光活性进行了筛选。虽然 Tr(Me)的溶液没有发光，但 7 仅在 77 K 时发光，而 5 在 r.t.和 77 K 时都发光。
