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首页> 外文期刊>Chemistry: A European journal >Synthesis, Structure, and Physico-optical Properties of Manganate(II)-Based Ionic Liquids
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Synthesis, Structure, and Physico-optical Properties of Manganate(II)-Based Ionic Liquids

机译：锰酸根（II）离子液体的合成，结构和物理光学性质

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摘要

Several ionic liquids (ILs) based on complex manganate(II) anions with chloro, bromo, and bis(trifluoromethanesulfonyl)amido (Tf2N) ligands have been synthesized. As counterions, n-alkyl-methylimidazolium (C(n)mim) cations of different chain length (alkyl = ethyl (C,), propyl (C-3), butyl (C-4), hexyl (C-6)) were chosen. Except for the 1-hexyl-3-methylimidazolium ILs, all of the prepared compounds could be obtained in a crystalline state at room temperature. However, each of the compounds displayed a strong tendency to form a supercooled liquid. Generally, solidification via a glass transition took place below -40 degrees C. Consequently, all of these compounds can be regarded as ionic liquids. Depending on the local coordination environment of Mn2+, green (tetrahedrally coordinated Mn2+) or red (octahedrally coordinated Mn2+) luminescence emission from the T-4(G) level is observed.([1]) The local coordination of the luminescent Mn2+ centre has been unequivocally established by UV/Vis as well as Raman and IR vibrational spectroscopies. Emission decay times measured at room temperature in the solid state (crystalline or powder) were generally a few ms, although, depending on the ligand, values of up to 25 ms were obtained. For the bromo compounds, the luminescence decay times proved to be almost independent of the physical state and the temperature. However, for the chloro- and bis(trifluoromethanesulfonyl)amido ILs, the emission decay times were found to be dependent on the temperature even in the solid state, indicating that the measured values are strongly influenced by nuclear motion and the vibration of the atoms. In the liquid state, the luminescence of tetrahedrally coordinated Mn2+ could only be observed when the tetrachloromanganate ILs were diluted with the respective halide ILs. However, for [C(3)mim][Mn(Tf2N)(3)], in which Mn2+ is in an octahedral coordination environment, a weak red emission from the pure compound was found even in the liquid state at elevated temperatures.
机译：已经合成了几种基于复杂锰酸根（II）阴离子与氯，溴和双（三氟甲磺酰基）酰胺基（Tf2N）配体的离子液体（ILs）。作为抗衡离子，不同链长的正烷基甲基咪唑鎓（C（n）mim）阳离子（烷基=乙基（C，），丙基（C-3），丁基（C-4），己基（C-6））被选中。除了1-己基-3-甲基咪唑鎓IL，所有制备的化合物都可以在室温下以结晶状态获得。然而，每种化合物显示出形成过冷液体的强烈趋势。通常，通过玻璃化转变的固化发生在-40℃以下。因此，所有这些化合物都可以视为离子液体。根据Mn2 +的局部配位环境，观察到T-4（G）的绿色（四面体配位的Mn2 +）或红色（八面体配位的Mn2 +）发光。[[1]）发光Mn2 +中心的局部配位具有由UV / Vis以及拉曼和IR振动光谱法明确建立。固态（晶体或粉末）在室温下测得的发射衰减时间通常为几毫秒，尽管根据配体的不同，可以获得高达25毫秒的值。对于溴化合物，发光衰减时间证明几乎与物理状态和温度无关。但是，对于氯和双（三氟甲磺酰基）酰胺基离子液体，即使在固态下，其发射衰减时间也取决于温度，这表明测量值受核运动和原子振动的强烈影响。在液态下，只有用相应的卤化物IL稀释四氯锰酸盐IL才能观察到四面体配位的Mn2 +的发光。但是，对于[C（3）mim] [Mn（Tf2N）（3）]，其中Mn2 +在八面体配位环境中，即使在高温下呈液态，也发现来自纯化合物的微弱红色发射。

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