Crystalline-state cis-to-trans transformation of a two-dimensional spin-crossover system.-猫眼课题宝

DOI：

10.1002/chem.201003359

发表时间：

2011-02

期刊：

Chemistry

影响因子：

通讯作者：

中科院分区：

文献类型：

作者：

Xin Bao;Peng-Hu Guo;Jun‐Liang Liu;Ji-Dong Leng;M. Tong

与结晶态配位聚合物(CP)相关的超分子结构转变是一个很有前途的研究方向，不仅因为它们可以提供直接的证据来帮助理解拓扑化学反应，而且还因为伴随着物理/化学性质的调节，如磁、光和手性行为，这有助于深入了解结构和磁性之间的关系。与仅由客体移除/包裹体引发的相对常见的晶体转变相比，涉及网络连接性的剧烈重组的[1，2]转变，如穿透/维度的变化和特殊的原子运动，更有可能提供具有完全不同性质的新相，因此更令人着迷。然而，涉及这种转变的例子很少，主要是由于在大的结构重排后很难保持结晶度，因此对随后的物理/化学性质变化的进一步研究更加缺乏。自旋交叉(SCO)材料由于其响应外界刺激(如温度、压力或光)在高自旋(HS)和低自旋(LS)状态之间的自旋转变(STS)而被潜在地应用于分子存储器、分子开关、分子传感器、数据存储和显示器件。5]在结构可变的配位聚合物中加入上海合作组织的构建块将是非常有趣的，因为结构转换过程很可能导致上海合作组织行为的巨大变化。本文报道了二维FeII/2，4-Hbpt体系(2，4-Hbpt=3-(2-吡啶)-5-(4-吡啶)-1，2，4-三唑)SCO体系的热驱动超分子异构化反应，其结构从顺式[FeIIACHTUNGTRENUNG(2，4-bpt)2]·4H2O(1)转变为反式[FeIIACHTUNGTRENUNG(2，4-bpt)2](2)。在转变过程中发生了几个主要的变化：1)2，4-BPT配体对金属的配位构型

Supramolecular structural transformations involving coordination polymers (CP) in the crystalline state form an promising body of research, not only because they can provide direct proof which helps understand topochemical reactions, but also due to the accompanied modulation of physical/chemical properties, such as magnetic, optical, and chiral behavior, which helps gain insights into the correlation between structural and magnetic properties. In contrast to the relatively common crystal transformation triggered solely by guest removal/inclusion,[1, 2] transformation involving drastic reorganization of the network connectivity, such as change of interpenetration/dimensionality and special atom movements, is more likely to provide new phases with totally different properties thus is more fascinating. However, rare examples have been reported involving such transformations,[3] mainly due to the difficulty to maintain crystallinity after a large structural rearrangement, and thus further investigations on the subsequent physical/chemical property changes are more scarce.Spin-crossover (SCO) materials have potential applications as molecular memories, molecular switches, molecular sensors, data storage, and display devices due to their spin transitions (STs) between high-spin (HS) and low-spin (LS) states in response to external stimuli such as temperature, pressure, or light.[4, 5] Incorporation of SCO building blocks in a structural changeable coordination polymer will be quite intriguing as the structural transformation process is very likely to cause dramatic change of SCO behaviors. Herein we report a thermal-driven supramolecular isomerization in the two-dimensional (2D) FeII/2, 4-Hbpt system (2, 4-Hbpt= 3-(2-pyridyl)-5-(4-pyridyl)-1, 2, 4-triazole) SCO system with a dramatic structural transformation from cis-[FeIIACHTUNGTRENNUNG (2, 4-bpt) 2]· 4 H2O (1) to trans-[FeIIACHTUNGTRENNUNG (2, 4-bpt) 2](2). Several major changes occur during the transformation: 1) the coordination configurations of 2, 4-bpt ligands to the metal

Crystalline-state cis-to-trans transformation of a two-dimensional spin-crossover system.

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