Low-Dimensional Magnetism in Multivariate Copper/Zinc MOF-74 Materials Formed via Different Mechanochemical Methods

Muratović, Senada; Martinez, Valentina; Karadeniz, Bahar; Pajić, Damir; Brekalo, Ivana; Arhangelskis, Mihails; Mazaj, Matjaž; Mali, Gregor; Etter, Martin; Friščić, Tomislav; Krupskaya, Yulia; Kataev, Vladislav; Žilić, Dijana; Užarević, Krunoslav (2022) Low-Dimensional Magnetism in Multivariate Copper/Zinc MOF-74 Materials Formed via Different Mechanochemical Methods. Inorganic chemistry, 61 (45). pp. 18181-18192. ISSN 0020-1669

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Official URL: https://pubs.acs.org/doi/full/10.1021/acs.inorgche...

Abstract

MOF-74 is an archetypal magnetic metal−organic framework (MOF) family, with metal nodes bridged by 2, 5-dioxido-1, 4-benzenedicarboxylic acid (H4dobdc) 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.

Item Type:

Article

Uncontrolled Keywords:

MOF ; MOF-74 ; Cu(II) ; Zn(II) ; EPR ; ESR ; magnetism

Subjects:

NATURAL SCIENCES > Physics
NATURAL SCIENCES > Chemistry > Inorganic Chemistry

Divisions:

Division of Physical Chemistry

Projects:

Project title	Project leader	Project code	Project type
Studija važnosti spinskih međudjelovanja kao osnova za nove pristupe u istraživanju materijala	Ilakovac-Kveder, Marina	IP-2018-01-3168	HRZZ
Magneto-strukturne korelacije u molekulskim magnetskim kompleksima istraživane spektroskopijom elektronske spinske rezonancije	Žilić, Dijana	910-08/18-01/00324	MZO
utjecaj magnetske anziotropije na kvantne spinske sustave	Herak, Mirta	UIP-2014-09-9775	HRZZ
Mehanokemijske i bezotopinske strategije za sintezu funkcionalnih poroznih materijala s naprednim fizičko-kemijskim i katalitičkim svojstvima	Užarević, Krunoslav	PZS-2019-02-4129	HRZZ
Centar za Napredna Istraživanja Kompleksnih Sustava	Grbić, Mihael Srđan; Tafra, Emil	KK.01.1.1.02.0013	EK