Exploring Dipolar Dynamics and Ionic Transport in Metal‐Organic Frameworks: Experimental and Theoretical Insights

Abstract

The present study examines the potential coupling between dipolar dynamics and ionic charge transport in metal‐organic framework (MOF) compounds. MOFs are known for their high porosity and customizable properties. By integrating freely rotating dipolar groups into the ligands, a novel structure, CFA‐25, akin to the known BUT‐2 framework, is synthesized. This facilitated the investigation of local and macroscopic effects, particularly the possible interplay between dipolar units and Cs cations. The research aimed to understand fundamental dipolar dynamics and ionic charge transport, employing Cs ions for their X‐ray diffraction characterizability. Experimental analysis using dielectric spectroscopy, complemented by theoretical simulations, explored questions regarding glassy freezing of re‐orientational dynamics, Cs cation motion within the network, and the influence of dipolar units on transport. Contrary to previous reports, this work finds that Cs transport exhibits substantial barriers, necessitating specialized simulation techniques for accurate characterization. This interdisciplinary approach sheds light on the intricate dynamics of MOFs and offers insights into their potential applications involving ion transport phenomena.