Reversible On-Off Switching of a Single-Molecule Magnet via a Crystal-to-Crystal Chemical Transformation
Reversible On-Off Switching of a Single-Molecule Magnet via a Crystal-to-Crystal Chemical Transformation
复制标题
通过晶体到晶体的化学转化实现单分子磁体的可逆开关
DOI：
10.1021/jacs.7b07008
复制
发表时间：
2017
影响因子：
15
通讯作者：
Xin-Yi Wang
中科院分区：
文献类型：
--
作者：
Dong-Qing Wu;Dong Shao;Xiao-Qin Wei;Fu-Xing Shen;Le Shi;David Kempe;Yuan-Zhu Zhang;Kim R Dunbar;Xin-Yi Wang
动态分子晶体由于其潜在的应用前景而备受关注。本文报道了[Mo(CN)7]4基分子化合物中单分子磁体（SMM）的可逆开关行为。在脱水和再水合作用下，三核Mn2Mo分子[Mn(L)(H2O)]2[Mo(CN)7]·2H2O(1)发生可逆的晶体-晶体转变为六核mn4mo2化合物[Mn(L)(H2O)]2[Mn(L)]2[Mo(CN)7]2(2)。这种结构转变涉及到配位键的断裂和重整，从而导致颜色和磁性质的显著变化。化合物1是一个具有44.9 cm-1能量势垒的SMM，而化合物2虽然具有较高的基态自旋值，但表现为一个简单的顺磁体。[Mo(CN)7]4 - in2的五边形双锥体几何变形破坏了导致SMM行为的各向异性交换相互作用。
Dynamic molecular crystals are of high interest due to their potential applications. Herein we report the reversible on–off switching of single-molecule magnet (SMM) behavior in a [Mo(CN)7]4–based molecular compound. Upon dehydration and rehydration, the trinuclear Mn2Mo molecule [Mn(L)(H2O)]2[Mo(CN)7]·2H2O (1) undergoes reversible crystal-to-crystal transformation to a hexanuclear Mn4Mo2compound [Mn(L)(H2O)]2[Mn(L)]2[Mo(CN)7]2(2). This structural transformation involves the breaking and reforming of coordination bonds which leads to significant changes in the color and magnetic properties. Compound1is an SMM with an energy barrier of 44.9 cm–1, whereas2behaves as a simple paramagnet despite its higher ground state spin value. The distortion of the pentagonal bipyramidal geometry of [Mo(CN)7]4–in2disrupts the anisotropic exchange interactions that lead to SMM behavior in1.