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首页> 外文期刊>Chemistry: A European journal >(1-Butyl-4-methyl-pyridinium)[Cu(SCN)_2]: A Coordination Polymer and Ionic Liquid
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(1-Butyl-4-methyl-pyridinium)[Cu(SCN)_2]: A Coordination Polymer and Ionic Liquid

机译：（1-丁基-4-甲基-吡啶鎓）[Cu（SCN）_2]：配位聚合物和离子液体

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摘要

The compound (C_4C_1py)[Cu(SCN)_2], (C_4py = 1-Butyl-4-methyl-pyridinium), which can be obtained from CuSCN and the ionic liquid (C_4C_1py)(SCN), turns out to be a new organic-inorganic hybrid material as it qualifies both, as a coordination polymer and an ionic liquid. It features linked [Cu(SCN)_2]~- units, in which the thiocyanates bridge the copper ions in a μ_(1,3)-fashion. The resulting one-dimen-sional chains run along the a axis, separated by the C_4C_1py counterions. Powder X-ray diffraction not only confirms the single-crystal X-ray structure solution but proves the reformation of the coordination polymer from an isotropic melt. However, the materials shows a complex thermal behavior often encountered for ionic liquids such as a strong tendency to form a supercooled melt. At a relatively high cooling rate, glass formation is observed. When heating this melt in differential scanning calorimetry (DSC) and temperature-dependent polarizing optical microscopy (POM), investigations reveal the existence of a less thermodynamically stable crystalline polymorph. Raman measurements conducted at 10 and 100°C point towards the formation of polyanionic chain fragments in the melt. Solid-state UV/Vis spectroscopy shows a broad absorption band around 18870 cm~(-1) (530 nm) and another strong one below 20000 cm~(-1) (< 500 nm). The latter is attributed to the d(Cu~I)→π*(SCN)-MLCT (metaI-to-ligand charge transfer) transition within the coordination polymer yielding an energy gap of 2.4 eV. At room temperature and upon irradiation with UV light, the material shows a weak fluorescence band at 15870 cm~(-1) (630 nm) with a quantum efficiency of 0.90(2) % and a lifetime of 131(2) ns. Upon lowering the temperature, the luminescence intensity strongly increases. Simultaneously, the band around 450 nm in the excitation spectrum decreases.
机译：可以从CuSCN和离子液体（C_4C_1py）（SCN）获得的化合物（C_4C_1py）[Cu（SCN）_2]（C_4py = 1-丁基-4-甲基-吡啶鎓）有机-无机杂化材料同时具备配位聚合物和离子液体的资格。它具有链接的[Cu（SCN）_2]〜-单元，其中的硫氰酸盐以μ_（1,3）形式桥接铜离子。生成的一维链沿着a轴延伸，并被C_4C_1py抗衡离子隔开。粉末X射线衍射不仅证实了单晶X射线结构溶液，而且证明了由各向同性的熔体对配位聚合物的重整。然而，该材料表现出离子液体经常遇到的复杂的热行为，例如形成过冷熔体的强烈趋势。在较高的冷却速率下，观察到玻璃形成。当在差示扫描量热法（DSC）和与温度相关的偏振光学显微镜（POM）中加热该熔体时，研究表明存在热力学较不稳定的结晶多晶型物。在10和100°C下进行的拉曼测量表明在熔体中形成了聚阴离子链片段。固态UV / Vis光谱显示在18870 cm〜（-1）（530 nm）附近有一个较宽的吸收带，而在20000 cm〜（-1）（<500 nm）以下则有一个很强的吸收带。后者归因于配位聚合物内的d（Cu〜I）→π*（SCN）-MLCT（金属到配体的电荷转移）跃迁，产生2.4 eV的能隙。在室温和紫外线照射下，该材料在15870 cm〜（-1）（630 nm）处显示弱的荧光带，量子效率为0.90（2）％，寿命为131（2）ns。降低温度，发光强度急剧增加。同时，激发光谱中450nm附近的谱带减小。

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