Dynamics of Linkers in Metal–Organic Framework Glasses | Sciact - CRIS-system of Boreskov Institute of Catalysis

Dynamics of Linkers in Metal–Organic Framework Glasses Full article

Journal

Journal of the American Chemical Society
ISSN: 0002-7863 , E-ISSN: 1520-5126

Output data

Year: 2024, Volume: 146, Number: 19, Pages: 12950–12957 Pages count : 8 DOI: 10.1021/jacs.3c13156

Tags

Amorphous materials, Crystals, Metal organic frameworks, Molecular dynamics, Nuclear magnetic resonance spectroscopy

Authors

Khudozhitkov Alexander E. ¹ , Ogiwara Naoki ^2,3 , Donoshita Masaki ^3,4 , Kobayashi Hirokazu ^3,5 , Stepanov Alexander G. ¹ , Kolokolov Daniil I. ¹ , Kitagawa Hiroshi ³

Affiliations

1	Boreskov Institute of Catalysis, Siberian Branch of Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
2	Department of Basic Science, School of Arts and Sciences, The University of Tokyo, Komaba, Meguro-ku, Tokyo 153-8902, Japan
3	Division of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-ku, Kyoto 606-8502, Japan
4	Institute for Materials Chemistry and Engineering, Kyushu University, Motooka 744, Nishi-ku, Fukuoka 819-0395, Japan
5	Research Center for Negative Emissions Technologies (K-NETs), Kyushu University, Motooka 744, Nishi-ku, Fukuoka 819-0395, Japan

Funding (4)

1	Ministry of Science and Higher Education of the Russian Federation	FWUR-2024-0032
2	Japan Society for the Promotion of Science	JP20H05623
3	Japan Society for the Promotion of Science	JP23H04613
4	Japan Society for the Promotion of Science	JP23K13759

Metal–organic framework (MOF) glasses have emerged as a new class of organic–inorganic hybrid glass materials. Considerable efforts have been devoted to unraveling the macroscopic dynamics of MOF glasses by studying their rheological behavior; however, their microscopic dynamics remain unclear. In this work, we studied the effect of vitrification on linker dynamics in ZIF-62 by solid-state 2H nuclear magnetic resonance (NMR) spectroscopy. 2H NMR relaxation analysis provided a detailed picture of the mobility of the ZIF-62 linkers, including local restricted librations and a large-amplitude twist; these details were verified by molecular dynamics. A comparison of ZIF-62 crystals and glasses revealed that vitrification does not drastically affect the fast individual flipping motions with large-amplitude twists, whereas it facilitates slow cooperative large-amplitude twist motions with a decrease in the activation barrier. These observations support the findings of previous studies, indicating that glassy ZIF-62 retains permanent porosity and that short-range disorder exists in the alignment of ligands because of distortion of the coordination angle.

Khudozhitkov A.E. , Ogiwara N. , Donoshita M. , Kobayashi H. , Stepanov A.G. , Kolokolov D.I. , Kitagawa H.
Dynamics of Linkers in Metal–Organic Framework Glasses
Journal of the American Chemical Society. 2024. V.146. N19. P.12950–12957. DOI: 10.1021/jacs.3c13156 WOS Scopus РИНЦ AN PMID OpenAlex

Submitted:	Nov 23, 2023
Accepted:	Apr 22, 2024
Published online:	May 2, 2024
Published print:	May 15, 2024

Web of science:	WOS:001227597600001
Scopus:	2-s2.0-85192224312
Elibrary:	67642426
Chemical Abstracts:	2024:960486
PMID:	38693778
OpenAlex:	W4396585594

DB	Citing
Scopus	2
Web of science	2