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[(CH2)3NH2][Zn(HCOO)3]中压力和温度诱导的相变的拉曼光谱和红外光谱研究

Raman and IR studies of pressure- and temperature-induced phase transitions in [(CH2)3NH2][Zn(HCOO)3].

作者信息

Mączka Mirosław, da Silva Tercio Almeida, Paraguassu Waldeci, Ptak Maciej, Hermanowicz Krzysztof

机构信息

Institute of Low Temperature and Structure Research, Polish Academy of Sciences , Box 1410, 50-950 Wrocław 2, Poland.

出版信息

Inorg Chem. 2014 Dec 1;53(23):12650-7. doi: 10.1021/ic502426x. Epub 2014 Nov 14.

Abstract

Temperature- and pressure-dependent studies of Raman and IR spectra have been performed on azetidinium zinc formate, [(CH2)3NH2][Zn(HCOO)3]. Vibrational spectra showed distinct anomalies in mode frequencies and bandwidths near 250 and 300 K, which were attributed to structural phase transitions associated with the gradual freezing of ring-puckering motions of the azetidinium cation. Pressure-dependent studies revealed a pressure-induced transition near 0.4 GPa. Raman spectra indicate that the structure of the room-temperature intermediate phase observed near 0.4 GPa is the same as the monoclinic structure observed at ambient pressure below 250 K. The second phase transition was found near 2.4 GPa. This transition has strong first-order character and is associated with strong distortion of both the zinc formate framework and azetidinium cations. The last phase transition was found near 7.0 GPa. This transition leads to lowering of the symmetry and further distortion of the zinc formate framework, whereas the azetidinium cation structure is weakly affected.

摘要

已对甲酸氮杂环丁烷锌盐[(CH2)3NH2][Zn(HCOO)3]进行了拉曼光谱和红外光谱的温度及压力依赖性研究。振动光谱显示在250和300 K附近的模式频率和带宽存在明显异常,这归因于与氮杂环丁烷阳离子环扭曲运动逐渐冻结相关的结构相变。压力依赖性研究揭示了在0.4 GPa附近的压力诱导转变。拉曼光谱表明,在0.4 GPa附近观察到的室温中间相结构与在250 K以下常压下观察到的单斜结构相同。在2.4 GPa附近发现了第二次相变。该转变具有强烈的一级特征,并且与甲酸锌骨架和氮杂环丁烷阳离子的强烈畸变有关。最后一次相变在7.0 GPa附近被发现。该转变导致对称性降低和甲酸锌骨架的进一步畸变,而氮杂环丁烷阳离子结构受到的影响较弱。

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