학술논문
Benzothiadiazole-based rotation and possible antipolar order in carboxylate-based metal-organic frameworks.
Document Type
Academic Journal
Author
Schnabel J; Chair of Solid State and Materials Chemistry, University of Augsburg, Institute of Physics, Universitaetsstrasse 1, 86159, Augsburg, Germany.; Schulz A; Experimental Physics V, Center for Electronic Correlations and Magnetism, University of Augsburg, Institute of Physics, Universitaetsstrasse 1, 86159, Augsburg, Germany.; Lunkenheimer P; Experimental Physics V, Center for Electronic Correlations and Magnetism, University of Augsburg, Institute of Physics, Universitaetsstrasse 1, 86159, Augsburg, Germany.; Volkmer D; Chair of Solid State and Materials Chemistry, University of Augsburg, Institute of Physics, Universitaetsstrasse 1, 86159, Augsburg, Germany. dirk.volkmer@physik.uni-augsburg.de.
Source
Publisher: Springer Nature Country of Publication: England NLM ID: 101725670 Publication Model: Electronic Cited Medium: Internet ISSN: 2399-3669 (Electronic) Linking ISSN: 23993669 NLM ISO Abbreviation: Commun Chem Subsets: PubMed not MEDLINE
Subject
Language
English
Abstract
By modifying organic ligands of metal-organic framework with dipolar units, they turn suitable for various applications, e.g., in the field of sensor systems or switching of gas permeation. Dipolar linkers in the organic ligand are capable to rotate in certain temperature and frequency ranges. The copper-bearing paddlewheel shaped metal-organic frameworks ZJNU-40 and JLU-Liu30 possess such a polarizable dipole moment due to their benzothiadiazole moiety in the organic ligands. Here, we investigate the molecular rotor behavior of benzothiadiazole units of the two carboxylate-based MOFs by dielectric spectroscopy and computational simulation. Our dielectric results provide clear evidence for significant reorientational relaxation dynamics of these rotors, revealing various characteristics of glasslike freezing upon cooling. The calculated rotational energy barriers are consistent with experimentally determined barriers for single-dipole dynamics. Moreover, for JLU-Liu30 we find hints at antipolar ordering below about 300 K.
(© 2023. The Author(s).)
(© 2023. The Author(s).)