Zhou Hao-Long, Zhang Yue-Biao, Zhang Jie-Peng, Chen Xiao-Ming
MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China.
1] MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China [2] School of Physical Science and Technology, ShanghaiTech University, 100 Haike Road, Shanghai 201210, China.
Nat Commun. 2015 Apr 21;6:6917. doi: 10.1038/ncomms7917.
The dynamic behaviours of host frameworks and guest molecules have received much attention for their great relevance with smart materials, but little has been developed to control or understand the host-guest interplay. Here we show that the confined guest can utilize not only molecular static effects but also bulk dynamic properties to control the host dynamics. By virtue of the three-dimensional hinge-like framework and quasi-discrete ultramicropores, a flexible porous coordination polymer exhibits not only drastic guest-modulation effect of the thermal expansion magnitude (up to 422 × 10(-6) K(-1)) and even the anisotropy but also records positive/negative thermal expansion coefficients of +482/-218 × 10(-6) K(-1). Moreover, single-crystal X-ray diffraction analyses demonstrate that the jack-like motion of the guest supramolecular dimers, being analogous to the anisotropic thermal expansion of bulk van der Waals solids, is crucial for changing the flexibility mode and thermal expansion behaviour of the crystal.
主体框架和客体分子的动态行为因其与智能材料的高度相关性而备受关注，但在控制或理解主客体相互作用方面进展甚微。在此，我们表明受限客体不仅可以利用分子静态效应，还可以利用整体动态性质来控制主体动力学。借助三维铰链状框架和准离散超微孔，一种柔性多孔配位聚合物不仅表现出热膨胀幅度（高达422×10(-6) K(-1)）甚至各向异性的剧烈客体调制效应，还记录了+482/-218×10(-6) K(-1)的正/负热膨胀系数。此外，单晶X射线衍射分析表明，客体超分子二聚体的千斤顶状运动类似于体相范德华固体的各向异性热膨胀，对于改变晶体的柔性模式和热膨胀行为至关重要。
