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Unusual and Tunable Negative Linear Compressibility in the Metal–Organic Framework MFM-133(M) (M = Zr, Hf)
Journal of the American Chemical Society ( IF 15.0 ) Pub Date : 2018-02-02 , DOI: 10.1021/jacs.7b11747
Yong Yan 1 , Alice E. O’Connor 2 , Gopikkaa Kanthasamy 2 , George Atkinson 2 , David R. Allan 3 , Alexander J. Blake 2 , Martin Schröder 1
Affiliation  

High-pressure single-crystal X-ray structural analyses of isostructural MFM-133(M) (M = Zr, Hf) of flu topology and incorporating the tetracarboxylate ligand TCHB4- [H4TCHB = 3,3',5,5'-tetrakis(4-carboxyphenyl)-2,2',4,4',6,6'-hexamethyl-1,1'-biphenyl] and {M6(μ3-OH)8(OH)8(COO)8} clusters confirm negative linear compressibility (NLC) behavior along the c axis. This occurs via a three-dimensional wine-rack NLC mechanism leading to distortion of the octahedral cage toward a more elongated polyhedron under static compression. Despite the isomorphous nature of these two structures, MFM-133(Hf) shows a higher degree of NLC than the Zr(IV) analogue. Thus, for the first time, we demonstrate here that the NLC property can be effectively tuned in a framework material by simply varying the inorganic component of the frameworks without changing the network topology and structure.

中文翻译:

金属-有机框架 MFM-133(M) (M = Zr, Hf) 中异常且可调的负线性压缩率

氟拓扑结构的同构 MFM-133(M) (M = Zr, Hf) 的高压单晶 X 射线结构分析,并结合了四羧酸配体 TCHB4- [H4TCHB = 3,3',5,5'-tetrakis (4-羧基苯基)-2,2',4,4',6,6'-六甲基-1,1'-联苯]和{M6(μ3-OH)8(OH)8(COO)8}簇确认沿 c 轴的负线性压缩率 (NLC) 行为。这是通过三维酒架 NLC 机制发生的,导致八面体笼在静态压缩下向更细长的多面体变形。尽管这两种结构具有同晶性质,但 MFM-133(Hf) 显示出比 Zr(IV) 类似物更高程度的 NLC。于是,第一次,
更新日期:2018-02-02
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