Unfolding the terahertz spectrum of soft porous crystals: rigid unit modes and their impact on phase transitions

A.E.J. Hoffman, I. Senkovska, J. Wieme, A. Krylov, S. Kaskel, V. Van Speybroeck
Journal of Materials Chemistry A
2022
A1

Abstract 

Phase transitions in exible metal-organic frameworks or soft porous crystals are mediated by low-frequency phonons or rigid-unit modes. The alteration of specic building blocks may change the lattice dynamics of these frameworks, which can inuence the phase transition mechanism. In this work, the impact of building block substitution on the rigid-unit modes in exible MIL-53 analogs with a winerack topology will be investigated via ab initio lattice dynamics calculations. First, the accuracy of the theoretical simulations is veried via experimental Raman measurements, which provide unique ngerprint vibrations in the terahertz range to characterize the phase transition. Following analysis of the low-frequency vibrations shows that there exists a set of universal rigid-unit modes inducing translations and/or rotations of the building blocks. The theoretical results demonstrate that linker substitutions have a large eect on the rigid-unit mode frequencies, whereas this is less so for inorganic chain substitutions. These ndings may help to rationally tune the phonon frequencies in soft porous crystals.