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 jul 2020
Accepted
27 aug 2020
First published
28 aug 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

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements