Guest-dependent high pressure phenomena in a nanoporous metal-organic framework material

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Chapman, Karena W. [1 ]
Halder, Gregory J. [2 ]
Chupas, Peter J. [1 ]
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[1] X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, IL 60439, United States
[2] Materials Science Division, Argonne National Laboratory, Argonne, IL 60439, United States
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The nanoporous metal-organic framework material Cu3(1,3,5-benzenetricarboxylate)2(H2O)3•{guest} exhibits anomalous compression under applied pressure that is associated with the hyper-filling of the pore network. This behavior involves a dramatic transition between a hard regime (bulk modulus, Khard 118 GPa), where the pressure-transmitting fluid penetrates the framework cavities, and a soft regime (Ksoft 30 GPa), where the guest-framework system compresses concertedly. Not only is the duality in compressibility triggered by the availability of potential guests but the size/penetrability of the guest molecules determines the pressure at which the hard-soft transition occurs. Specifically, the observed compression behavior depends on the size of the pressure-transmitting fluid molecules, the sample particle size (i.e., the extent of the pore network), and the rate at which the pressure is increased. The unprecedentedpressure-induced phenomena documented here, illustrates the exotic high-pressure behaviors possible in this versatile class of advanced functional materials with broad implications for their structure-function relationships and accordingly their practical application. Copyright © 2008 American Chemical Society;
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页码:10524 / 10526
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