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An organometallic half-sandwich supramolecular complex {K(18-Crown-6)(ηn-C6H5B(C6H5)3)} (n = 1–6) exhibiting a reversible breaking-symmetry phase transition and switchable dielectric behaviour

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Abstract

A supramolecular crystal, built from a 1 : 1 molar ratio of potassium tetraphenylboron (KBPh4) with 1,4,7,10,13,16-hexaoxacyclooctadecane (18-Crown-6), contains an organometallic half-sandwich superstructure unit {K(18-Crown-6)(ηn-C6H5B(C6H5)3)} (1 with n = 1–6), and shows a reversible phase transition at ∼211 K. The analysis of crystal structures at 173 K in the low-temperature phase, and 293 and 423 K in the high-temperature phase revealed that the breaking-symmetry phase transition is associated with the order–disorder transformation of [K(18-Crown-6)]+ and the change of the coordination mode of the phenyl ring to K+. A dielectric anomaly appears at ca. 212 K and dielectric relaxation occurs above 375 K in 1. The dielectric and thermal anomaly temperatures are close to each other, and the dielectric relaxation is relevant to the relative displacement of [K(18-Crown-6)]+ and the tetraphenylboron anion.

Graphical abstract: An organometallic half-sandwich supramolecular complex {K(18-Crown-6)(ηn-C6H5B(C6H5)3)} (n = 1–6) exhibiting a reversible breaking-symmetry phase transition and switchable dielectric behaviour

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Publication details

The article was received on 10 Oct 2018, accepted on 31 Oct 2018 and first published on 02 Nov 2018


Article type: Communication
DOI: 10.1039/C8DT04060E
Citation: Dalton Trans., 2018, Advance Article
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    An organometallic half-sandwich supramolecular complex {K(18-Crown-6)(ηn-C6H5B(C6H5)3)} (n = 1–6) exhibiting a reversible breaking-symmetry phase transition and switchable dielectric behaviour

    G. Yuan, D. Shao, Z. Yao, W. Liu and X. Ren, Dalton Trans., 2018, Advance Article , DOI: 10.1039/C8DT04060E

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