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The lone-pair-electron-driven phase transition and order-disorder processes in thermochromic (2-MIm)SbI4 organic-inorganic hybrid

Abstract

The easy to prepare and stable in air (2-methylimidazolium) tetraiodoantimoniate(III) single-crystals with optical band gap of 2.17(1) eV at room temperature have been synthesized. The crystal structure features one-dimensional [SbI4]-n anionic chains which are intercepted with stacks of 2MIm+ ions. At 294/295 K it undergoes structural phase transition to incommensurately modulated phase as a result of subtle, lone-pair-electron-driven distortions of the anionic part. Separately from the anion displacements the ordering of 2MIm+ countercations takes place over a wide temperature range of modulated phase. The disorder changes from dynamic to static around 200 K which affects the crystal structure leading to discontinues, step-like contraction of the lattice parameters. The material is thermochromic with prominent color changes, from raspberry to yellow at low temperatures. The calculated electronic structures and observed optical properties signpost its semiconducting character.

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Publication details

The article was received on 26 Sep 2017, accepted on 05 Nov 2017 and first published on 06 Nov 2017


Article type: Paper
DOI: 10.1039/C7DT03622A
Citation: Dalton Trans., 2017, Accepted Manuscript
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    The lone-pair-electron-driven phase transition and order-disorder processes in thermochromic (2-MIm)SbI4 organic-inorganic hybrid

    A. Gągor, G. Banach, M. Węławik, A. Piecha-Bisiorek and R. Jakubas, Dalton Trans., 2017, Accepted Manuscript , DOI: 10.1039/C7DT03622A

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