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一种可切换的分子转子:聚合物自旋交叉化合物的中子光谱研究。

A switchable molecular rotator: neutron spectroscopy study on a polymeric spin-crossover compound.

机构信息

Instituto de Ciencia de Materiales de Aragón (ICMA), CSIC-Universidad de Zaragoza, 50009 Zaragoza, Spain.

出版信息

J Am Chem Soc. 2012 Mar 21;134(11):5083-9. doi: 10.1021/ja206228n. Epub 2012 Mar 12.

Abstract

A quasielastic neutron scattering and solid-state (2)H NMR spectroscopy study of the polymeric spin-crossover compound {Fe(pyrazine)[Pt(CN)(4)]} shows that the switching of the rotation of a molecular fragment--the pyrazine ligand--occurs in association with the change of spin state. The rotation switching was examined on a wide time scale (10(-13)-10(-3) s) by both techniques, which clearly demonstrated the combination between molecular rotation and spin-crossover transition under external stimuli (temperature and chemical). The pyrazine rings are seen to perform a 4-fold jump motion about the coordinating nitrogen axis in the high-spin state. In the low-spin state, however, the motion is suppressed, while when the system incorporates benzene guest molecules, the movements of the system are even more restricted.

摘要

采用准弹性中子散射和固态(2)H NMR 光谱法研究了聚合物自旋交叉配合物{Fe(pyrazine)[Pt(CN)(4)]},结果表明分子片段(吡嗪配体)的旋转发生在自旋态变化的同时。两种技术都在很宽的时间范围内(10(-13)-10(-3) s)对旋转切换进行了研究,清楚地表明了分子旋转与外部刺激(温度和化学)下的自旋交叉跃迁之间的结合。在高自旋态下,吡嗪环沿配位氮轴进行 4 重跳跃运动。然而,在低自旋态下,运动受到抑制,而当系统包含苯客体分子时,系统的运动甚至受到更多限制。

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