Crystallographic Observation of Dynamic Gas Adsorption Sites and Thermal Expansion in a Breathable Fluorous Metal–Organic Framework


  • This work resulted from research support by the U. S. National Science Foundation (CHE-0349313), the Robert A. Welch Foundation (B-1542), the Texas Advanced Research Program (009741-0089-2007), and the U. S. Department of Energy (DE-FC26-06NT42859).


Playing accordion: Cooling a single crystal of a microporous fluorous metal–organic framework under ambient atmosphere leads to very large breathing upon gas adsorption, during which multiple N2 molecules are filled into channels and cages (see picture). While the framework exhibits remarkable positive thermal expansion under vacuum, a gigantic apparent negative thermal expansion takes place when the crystal is exposed to N2 at ambient pressure.

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