Issue 47, 2020

Relaxing under pressure with a rigid niccolite formate framework

Abstract

The rich dielectric properties of hybrid formate frameworks are tightly related to the dipolar dynamics and phase transitions of these compounds. A complete understanding of such phenomena requires experiments performed under non-standard conditions. Herein, we report high-pressure dielectric properties of anisotropic single crystals of a 1,4-diaminobutane zinc-formate framework [NH3(CH2)4NH3][Zn2(HCOO)6]. Experiments performed over wide temperature and pressure ranges allowed us to determine the equation of state of this compound. We reveal that a reversible structural phase transition, associated with a change of the crystal symmetry and partial ordering of the 1,4-diaminobutane cations, is characterized by a linear increase of the transition temperature with increasing pressure (dT0/dp = 5.8(2) K GPa−1). The X-ray diffraction and high-pressure dielectric experiments show that zinc cations together with formate anions form a rigid cage with crystal axis-dependent response to pressure, which affects the dynamics of 1,4-diaminobutane cations. We also demonstrate that the structural phase transition of this compound occurs at a constant value of the dielectric relaxation time (isochronic conditions) further revealing a tight relation between the framework and molecular cations. Our experimental results are supported by the molecular dynamics simulations.

Graphical abstract: Relaxing under pressure with a rigid niccolite formate framework

Supplementary files

Article information

Article type
Paper
Submitted
25 8 2020
Accepted
22 10 2020
First published
22 10 2020

J. Mater. Chem. C, 2020,8, 16736-16741

Relaxing under pressure with a rigid niccolite formate framework

A. Z. Szeremeta, A. Nowok, A. Sieradzki, M. Simenas, L. Vilčiauskas, A. Gągor, M. Mączka, M. Paluch and S. Pawlus, J. Mater. Chem. C, 2020, 8, 16736 DOI: 10.1039/D0TC04047A

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