Journal Article

PUBDB-2022-07726

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Low-Dimensional Magnetism in Multivariate Copper/Zinc MOF-74 Materials Formed via Different Mechanochemical Methods

Muratović, S. ; Martinez, V.Extern* ; Karadeniz, B.Extern* ; Pajić, D. ; Brekalo, I.Extern* ; Arhangelskis, M. ; Mazaj, M. ; Mali, G.Extern* ; Etter, M.DESY* ; Friščić, T.Extern* ; Krupskaya, Y. ; Kataev, V. ; Žilić, D. (Corresponding author) ; Uzarevic, K. (Corresponding author)Extern*

2022
American Chemical Society Washington, DC

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Please use a persistent id in citations: doi:10.1021/acs.inorgchem.2c02898  doi:10.3204/PUBDB-2022-07726

Abstract: MOF-74 is an archetypal magnetic metal–organic framework (MOF) family, with metal nodes bridged by 2,5-dioxido-1,4-benzenedicarboxylic acid (H$_4$dobdc) and arranged into one of the simplest representations of the 1D Ising magnetic model. Recently, a novel mechano-synthetic approach opened a pathway toward a series of bimetallic multivariate (1:1) M1M2-MOF-74 materials, with the uniform distribution of metal cations in the oxometallic chains, offering a unique opportunity to investigate low-dimensional magnetism in these heterometallic MOFs. We explore here how different mechanochemical procedures affect the interaction between the metal nodes of the model system of three multivariate copper(II)/zinc(II)-MOF-74 materials, two of which were obtained through a template-controlled procedure, and the third one was obtained by recently developed mechanical MOF-alloying combined with subsequent accelerated aging. While the three Cu/Zn-MOF-74 products have almost identical powder X-ray diffraction (PXRD) diffractograms and Fourier transform infrared spectra, they differ significantly in their magnetic properties, as revealed through detailed magnetization and X-band and multifrequency high-field electron spin resonance measurements. The magnetic results of the three multivariate Cu/Zn-MOF-74s were compared to the properties of the monometallic Cu-MOF-74, which shows antiferromagnetic intrachain and weaker ferromagnetic interchain interactions. Energy-dispersive X-ray spectroscopy/scanning electron microscopy and solid-state nuclear magnetic resonance spectroscopy helped rationalize the observed differences in magnetization, and in situ synchrotron PXRD monitoring of template-controlled MOF formation revealed different reaction pathways when using the zinc or copper intermediates, involving even the fleeting occurrence of a rare MOF-74 polymorph.

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Contributing Institute(s):

1. DOOR-User (DOOR ; HAS-User)
2. PETRA-D (FS-PETRA-D)

Research Program(s):

1. 632 - Materials – Quantum, Complex and Functional Materials (POF4-632) (POF4-632)
2. 6G3 - PETRA III (DESY) (POF4-6G3) (POF4-6G3)

Experiment(s):

1. PETRA Beamline P02.1 (PETRA III)

Appears in the scientific report 2022

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Database coverage:
; ; Clarivate Analytics Master Journal List ; Current Contents - Physical, Chemical and Earth Sciences ; Ebsco Academic Search ; Essential Science Indicators ; IF >= 5 ; JCR ; Nationallizenz ; SCOPUS ; Science Citation Index Expanded ; Web of Science Core Collection

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