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Issue 79, 2020
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Rotational dynamics of the imidazolium ion in cyanide-bridged dielectric framework materials

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Abstract

Reorientation of organic cations in the cubic interstices of cyanoelpasolite molecular perovskites results in a variety of structural phase transitions, but far less is known about these cations’ dynamics. We report quasielastic neutron scattering from the materials (C3H5N2)2K[MIII(CN)6], M = Fe,Co, which is directly sensitive to the rotation of the imidazolium ion. The motion is well described by a circular three-site hopping model, with the ion rotating within its plane in the intermediate-temperature phase, but tilting permanently in the high-temperature phase. Thus the two rhombohedral phases, which are crystallographically rather similar, have markedly different dynamics. The activation energy of rotation is about 10 kJ mol−1 and the barrier between orientations is 6 kJ mol−1. Our results explain two anomalous features in these materials’ dielectric constants.

Graphical abstract: Rotational dynamics of the imidazolium ion in cyanide-bridged dielectric framework materials

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Supplementary files

Article information


Submitted
31 Jul 2020
Accepted
27 Aug 2020
First published
28 Aug 2020

This article is Open Access

Chem. Commun., 2020,56, 11791-11794
Article type
Communication

Rotational dynamics of the imidazolium ion in cyanide-bridged dielectric framework materials

A. E. Phillips, G. Cai and F. Demmel, Chem. Commun., 2020, 56, 11791
DOI: 10.1039/D0CC05238H

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