Issue 79, 2020

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

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

Supplementary files

Article information

Article type
Communication
Submitted
31 iyl 2020
Accepted
27 avq 2020
First published
28 avq 2020
This article is Open Access
Creative Commons BY-NC license

Chem. Commun., 2020,56, 11791-11794

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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