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A high temperature reversible phase transition in a supramolecular complex of 15-crown-5 with tetraphenylboron sodium

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Abstract

A supramolecular crystal, [Na(15-crown-5)][BPh4] (1), (15-crown-5 = 1,4,7,10,13-pentaoxacyclopentadecane, NaBPh4 = sodium tetraphenylboron), has been obtained by mixing the ethanol solution of 15-crown-5 and NaBPh4 in the molar ratio of 1 : 1. The crystal structure was determined at 293 K, revealing that two [Na(15-crown-5)]+ cations form a supramolecular dimer via sharing one side-edge of coordination pentagonal pyramids; also, there are significant H-bonding interactions between anions and supramolecularly dimeric cations. Differential scanning calorimetry (DSC) showed that 1 undergoes a reversible first-order phase transition at ca. 391 K (Tc) upon heating, with a thermal hysteresis of 19 K. ΔH and ΔS were estimated to be 6.9 kJ mol−1 and 17.7 J mol−1 K−1, respectively, in the heating run. The variable-temperature powder X-ray diffraction and dielectric spectra were collected, and both disclosed no significant difference between the low- and high-temperature phases. These results suggest that the phase transition is an ordered–disordered type, which probably involves the change of anion configuration.

Graphical abstract: A high temperature reversible phase transition in a supramolecular complex of 15-crown-5 with tetraphenylboron sodium

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Publication details

The article was received on 02 Jun 2018, accepted on 30 Jul 2018 and first published on 31 Jul 2018


Article type: Paper
DOI: 10.1039/C8NJ02754D
Citation: New J. Chem., 2018, Advance Article
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    A high temperature reversible phase transition in a supramolecular complex of 15-crown-5 with tetraphenylboron sodium

    G. Yuan, S. Liu, Z. Tian and X. Ren, New J. Chem., 2018, Advance Article , DOI: 10.1039/C8NJ02754D

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