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Exceptional Framework Flexibility and Sorption Behavior of a Multifunctional Porous Cuprous Triazolate Framework
Abstract
The porous metal azolate framework [Cu(etz)]infinity (MAF-2, Hetz = 3,5-diethyl-1,2,4-triazole) processes an NbO type cuprous triazolate scaffold and a CsCl type hydrophobic channel system, in which the large cavities are interconnected by small apertures with pendant ethyl groups. Since the ethyl-blocked apertures behave as thermoactivated IRIS stops for the guest molecules, the gas sorption behavior of MAF-2 can be controlled by temperature, in which N2 adsorption was observed at 195 K rather than 77 K. Single-crystal X-ray structural analysis revealed that the [Cu(etz)]infinity host framework is not altered upon N2 inclusion, confirming the occurrence of the so-called " kinetically controlled flexibility". By virtue of the kinetically controlled flexibility and hydrophobic pore surface, MAF-2 can adsorb large amounts of small organic molecules but excludes H2O. As demonstrated by single-crystal X-ray structural analyses, MAF-2 shrinks, expands, or distorts its framework to accommodate the hydrogen-bonded hexamers of MeOH, EtOH, or MeCN, respectively. Moreover, MAF-2 can also separate benzene and cyclohexane efficiently, as its flexible scaffold can distort to a certain degree so that benzene can diffuse through the distorted apertures but cyclohexane cannot. Moreover, the adsorption/desorption of these organic vapors induces reversible, multimode structural transformations.
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Metadata
- Authors
- Zhang, J.-P., & Chen, X.-M.
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2008-04-03
- Volume
- 130
- Issue
- 18
- Pages
- 6010-6017
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W1987672211
- Cited by
- 502
- References
- 41
- FWCI
- 27.82
- Type
- journal article
- Language
- en
- Open access
- closed
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