Flexibility transition and guest-driven reconstruction in a ferroelastic metal–organic framework

The metal–organic framework copper( i ) tricyanomethanide, Cu(tcm), undergoes a ferroelastic transition on cooling below T f = 240 K. Thermal expansion measurements reveal an order-of-magnitude variation in framework flexibility across T f . The low-temperature phase α-Cu(tcm) exhibits colossal posi...

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Published inCrystEngComm Vol. 17; no. 2; pp. 361 - 369
Main Authors Hunt, Sarah J., Cliffe, Matthew J., Hill, Joshua A., Cairns, Andrew B., Funnell, Nicholas P., Goodwin, Andrew L.
Format Journal Article
LanguageEnglish
Published The Royal Society of Chemistry 01.01.2015
Subjects
Acetonitrile
Chemistry
Cooling
Flexibility
Heating
Infrared spectroscopy
Metal-organic frameworks
Phase change
Phase transformations
Thermal expansion
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Summary:The metal–organic framework copper( i ) tricyanomethanide, Cu(tcm), undergoes a ferroelastic transition on cooling below T f = 240 K. Thermal expansion measurements reveal an order-of-magnitude variation in framework flexibility across T f . The low-temperature phase α-Cu(tcm) exhibits colossal positive and negative thermal expansion that is the strongest ever reported for a framework material. On exposure to acetonitrile, Cu(tcm) undergoes a reconstructive solid-phase transition to acetonitrilocopper( i ) tricyanomethanide. This transition can be reversed by heating under vacuum. Infrared spectroscopy measurements are sensitive to the phase change, suggesting that Cu(tcm) may find application in solid-phase acetonitrile sensing.
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ISSN:1466-8033
1466-8033
DOI:10.1039/C4CE01572J