Exploring Spin-Phonon Coupling in Magnetic 2D Metal-Organic Frameworks

Overview

Journal Nanomaterials (Basel)

Date 2023 Apr 13

PMID 37049265

Authors

Diego Lopez-Alcala

Alberto M Ruiz

Jose J Baldovi

Affiliations

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Abstract

Layered magnetic metal-organic frameworks (MOFs) are an emerging class of materials that can combine the advantages of both MOFs and 2D magnetic crystals. The recent discovery of large coercivity and long-range magnetic ordering up to 515 K in a layered MOF of general formula MCl(pyz) (M = transition metal, pyz = pyrazine) offers an exciting versatile platform to achieve high-T magnetism at the 2D limit. In this work, we investigate the exfoliation feasibility down to the monolayer of VCl(pyz) and CrCl(pyz) by means of first-principles calculations. We explore their structural, electronic, magnetic and vibrational properties, as well as the effect of halide substitution. Then, we provide a full analysis of the spin-phonon coupling (SPC) in both 2D derivatives. Our calculations reveal a low SPC and thermal evolution of the magnetic exchange interactions and single-ion anisotropy mainly governed by low-frequency phonon modes. Finally, we provide chemical insights to improve the performance of these magnetic 2D MOFs based on the effective manipulation of the phonon modes that can present a major impact on their magnetic properties.

Citing Articles

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PMID: 38699254 PMC: 11062094. DOI: 10.1039/d4sc00823e.

References

Tanabe K, Cohen S . Postsynthetic modification of metal-organic frameworks--a progress report. Chem Soc Rev. 2010; 40(2):498-519. DOI: 10.1039/c0cs00031k. View

Lu J, Xu H, Yu H, Hu X, Xia J, Zhu Y . Ultrafast rectifying counter-directional transport of proton and metal ions in metal-organic framework-based nanochannels. Sci Adv. 2022; 8(14):eabl5070. PMC: 8985916. DOI: 10.1126/sciadv.abl5070. View

Dong R, Han P, Arora H, Ballabio M, Karakus M, Zhang Z . High-mobility band-like charge transport in a semiconducting two-dimensional metal-organic framework. Nat Mater. 2018; 17(11):1027-1032. DOI: 10.1038/s41563-018-0189-z. View

Tao J, Perdew J, Staroverov V, Scuseria G . Climbing the density functional ladder: nonempirical meta-generalized gradient approximation designed for molecules and solids. Phys Rev Lett. 2003; 91(14):146401. DOI: 10.1103/PhysRevLett.91.146401. View

Grimme S . Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J Comput Chem. 2006; 27(15):1787-99. DOI: 10.1002/jcc.20495. View

Furukawa H, Cordova K, OKeeffe M, Yaghi O . The chemistry and applications of metal-organic frameworks. Science. 2013; 341(6149):1230444. DOI: 10.1126/science.1230444. View

Liu C, Bai Y, Li W, Yang F, Zhang G, Pang H . In Situ Growth of Three-Dimensional MXene/Metal-Organic Framework Composites for High-Performance Supercapacitors. Angew Chem Int Ed Engl. 2022; 61(11):e202116282. DOI: 10.1002/anie.202116282. View

Thorarinsdottir A, Harris T . Metal-Organic Framework Magnets. Chem Rev. 2020; 120(16):8716-8789. DOI: 10.1021/acs.chemrev.9b00666. View

Barman A, Gubbiotti G, Ladak S, Adeyeye A, Krawczyk M, Grafe J . The 2021 Magnonics Roadmap. J Phys Condens Matter. 2021; 33(41). DOI: 10.1088/1361-648X/abec1a. View

10.

Song X, Wang X, Li Y, Zheng C, Zhang B, Di C . 2D Semiconducting Metal-Organic Framework Thin Films for Organic Spin Valves. Angew Chem Int Ed Engl. 2019; 59(3):1118-1123. DOI: 10.1002/anie.201911543. View

11.

Pedersen K, Perlepe P, Aubrey M, Woodruff D, Reyes-Lillo S, Reinholdt A . Formation of the layered conductive magnet CrCl(pyrazine) through redox-active coordination chemistry. Nat Chem. 2018; 10(10):1056-1061. DOI: 10.1038/s41557-018-0107-7. View

12.

Perdew . Density-functional approximation for the correlation energy of the inhomogeneous electron gas. Phys Rev B Condens Matter. 1986; 33(12):8822-8824. DOI: 10.1103/physrevb.33.8822. View

13.

Lopez-Cabrelles J, Manas-Valero S, Vitorica-Yrezabal I, Bereciartua P, Rodriguez-Velamazan J, Waerenborgh J . Isoreticular two-dimensional magnetic coordination polymers prepared through pre-synthetic ligand functionalization. Nat Chem. 2018; 10(10):1001-1007. DOI: 10.1038/s41557-018-0113-9. View

14.

Bjorkman T, Gulans A, Krasheninnikov A, Nieminen R . van der Waals bonding in layered compounds from advanced density-functional first-principles calculations. Phys Rev Lett. 2012; 108(23):235502. DOI: 10.1103/PhysRevLett.108.235502. View

15.

Damron J, Ma J, Kurz R, Saalwachter K, Matzger A, Ramamoorthy A . The Influence of Chemical Modification on Linker Rotational Dynamics in Metal-Organic Frameworks. Angew Chem Int Ed Engl. 2018; 57(28):8678-8681. PMC: 6289050. DOI: 10.1002/anie.201805004. View

16.

Liu H, Malissa H, Stolley R, Singh J, Groesbeck M, Popli H . Spin Wave Excitation, Detection, and Utilization in the Organic-Based Magnet, V(TCNE) (TCNE = Tetracyanoethylene). Adv Mater. 2020; 32(39):e2002663. DOI: 10.1002/adma.202002663. View

17.

Zhang R, Liu J, Gao Y, Hua M, Xia B, Knecht P . On-surface Synthesis of a Semiconducting 2D Metal-Organic Framework Cu (C O ) Exhibiting Dispersive Electronic Bands. Angew Chem Int Ed Engl. 2019; 59(7):2669-2673. DOI: 10.1002/anie.201913698. View

18.

Manriquez J, Yee G, McLean R, Epstein A, Miller J . A room-temperature molecular/organic-based magnet. Science. 1991; 252(5011):1415-7. DOI: 10.1126/science.252.5011.1415. View

19.

Maximoff S, Ernzerhof M, Scuseria G . Current-dependent extension of the Perdew-Burke-Ernzerhof exchange-correlation functional. J Chem Phys. 2004; 120(5):2105-9. DOI: 10.1063/1.1634553. View

20.

Escalera-Moreno L, Suaud N, Gaita-Arino A, Coronado E . Determining Key Local Vibrations in the Relaxation of Molecular Spin Qubits and Single-Molecule Magnets. J Phys Chem Lett. 2017; 8(7):1695-1700. DOI: 10.1021/acs.jpclett.7b00479. View