Phase and glass transitions observed by adiabatic calorimetry of host p-tert-butylcalix[4]arene and guest toluene inclusion crystal, suggesting the progress of the combined order-disorder process of the host-guest molecules

Kohei Ueda, Masaharu Oguni

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Abstract

Heat capacities of crystalline p-tert-butylcalix[4]arene·toluene host-guest compound were measured in a temperature range between 3 K and 345 K by adiabatic calorimetry. The crystal showed one second-order phase transition at 256.4 K accompanied by wide heat-capacity tails on both the high and low temperature sides and two first-order phase transitions with heat-capacity peaks at 127 K and 139 K. The total entropy of a sequence of the phase transitions was assessed experimentally to be 47 J K-1 mol-1, indicating that the number of allowed distinguishable molecular configurations is over 100 in the high-temperature disordered state. Many such distinguishable configurations are understood to be produced by a special intermolecular interaction of C-H⋯(π-electron) bonds formed between p-tert-butylcalix[4]arene and toluene molecules, and the transitions were interpreted as originating from orientational order-disorder of both the guest toluene molecule and the tert-butyl groups of host arene in their combination.

Original languageEnglish
Pages (from-to)11836-11842
Number of pages7
JournalJournal of Physical Chemistry B
Volume117
Issue number39
DOIs
Publication statusPublished - 3 Oct 2013

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