Low-Temperature Ferromagnetic Order in a Two-Level Layered Co Material

Overview

Journal Chem Mater

Date 2024 Sep 16

PMID 39279907

Authors

Patrick W Doheny

Gavin B G Stenning

Adam Brookfield

Fabio Orlandi

David Collison

Pascal Manuel

Sam T Carr

Paul J Saines

Affiliations

Soon will be listed here.

Abstract

The magnetic properties of a 2D layered material consisting of high-spin Co complexes, [Co(NHNH)(HO)Cl]Cl ( ), have been extensively characterized using electron paramagnetic resonance, magnetic susceptibility, and low-temperature heat capacity measurements. Electron paramagnetic resonance spectroscopy studies suggest that below 50 K, the = 3/2 orbital triplet state of Co is gradually depopulated in favor of the = 1/2 spin state, which is dominant below 20 K. In light of this, the magnetic susceptibility has been fitted with a two-level model, indicating that the interactions in this material are much weaker than previously thought. This two-level model is unable to fit the data at low temperatures and, combined with electron paramagnetic resonance spectroscopy, suggests that ferromagnetic interactions between Co cations in the = 1/2 state become significant approaching 2 K. Heat capacity measurements suggest the emergence of a long-range ordered state below 246 mK, which neutron diffraction confirms to be ferromagnetic.

References

Lancaster T, Huddart B, Williams R, Xiao F, Franke K, Baker P . Probing magnetic order and disorder in the one-dimensional molecular spin chains CuF(pyz) and [Ln(hfac)(boaDTDA)] (Ln = Sm, La) using implanted muons. J Phys Condens Matter. 2019; 31(39):394002. DOI: 10.1088/1361-648X/ab2cb6. View

RAMIREZ , Espinosa , Cooper . Strong frustration and dilution-enhanced order in a quasi-2D spin glass. Phys Rev Lett. 1990; 64(17):2070-2073. DOI: 10.1103/PhysRevLett.64.2070. View

Shapiro A, Landee C, Turnbull M, Jornet J, Deumal M, Novoa J . Synthesis, structure, and magnetic properties of an antiferromagnetic spin-ladder complex: bis(2,3-dimethylpyridinium) tetrabromocuprate. J Am Chem Soc. 2007; 129(4):952-9. DOI: 10.1021/ja066330m. View

Sampson G, Bristowe N, Carr S, Saib A, Stenning G, Clark E . Quantum Spin-1/2 Dimers in a Low-Dimensional Tetrabromocuprate Magnet. Chemistry. 2022; 28(32):e202200855. PMC: 9323490. DOI: 10.1002/chem.202200855. View

Balents L . Spin liquids in frustrated magnets. Nature. 2010; 464(7286):199-208. DOI: 10.1038/nature08917. View

Hoffmann S, Goslar J, Lijewski S . Electron Paramagnetic Resonance and Electron Spin Echo Studies of Co Coordination by Nicotinamide Adenine Dinucleotide (NAD) in Water Solution. Appl Magn Reson. 2013; 44(7):817-826. PMC: 3677979. DOI: 10.1007/s00723-013-0444-z. View

Boeer A, Barra A, Chibotaru L, Collison D, McInnes E, Mole R . A spectroscopic investigation of magnetic exchange between highly anisotropic spin centers. Angew Chem Int Ed Engl. 2011; 50(17):4007-11. DOI: 10.1002/anie.201100306. View

Liu H, Chaloupka J, Khaliullin G . Kitaev Spin Liquid in 3d Transition Metal Compounds. Phys Rev Lett. 2020; 125(4):047201. DOI: 10.1103/PhysRevLett.125.047201. View

Stoll S, Schweiger A . EasySpin, a comprehensive software package for spectral simulation and analysis in EPR. J Magn Reson. 2005; 178(1):42-55. DOI: 10.1016/j.jmr.2005.08.013. View

10.

Ivko S, Tustain K, Dolling T, Abdeldaim A, Mustonen O, Manuel P . Uncovering the Kagome Ferromagnet within a Family of Metal-Organic Frameworks. Chem Mater. 2022; 34(12):5409-5421. PMC: 9490827. DOI: 10.1021/acs.chemmater.2c00289. View

11.

Su S, Wu S, Baker M, Bencok P, Azuma N, Miyazaki Y . Quenching and Restoration of Orbital Angular Momentum through a Dynamic Bond in a Cobalt(II) Complex. J Am Chem Soc. 2020; 142(26):11434-11441. DOI: 10.1021/jacs.0c02257. View

12.

Mudiyanselage R, Wang H, Vilella O, Mourigal M, Kotliar G, Xie W . LiYbSe: Frustrated Magnetism in the Pyrochlore Lattice. J Am Chem Soc. 2022; 144(27):11933-11937. DOI: 10.1021/jacs.2c02839. View

13.

Shimizu Y, Miyagawa K, Kanoda K, Maesato M, Saito G . Spin liquid state in an organic Mott insulator with a triangular lattice. Phys Rev Lett. 2003; 91(10):107001. DOI: 10.1103/PhysRevLett.91.107001. View

14.

Caneschi A, Gatteschi D, Lalioti N, Sessoli R, Sorace L, Tangoulis V . Ising-type magnetic anisotropy in a cobalt(II) nitronyl nitroxide compound: a key to understanding the formation of molecular magnetic nanowires. Chemistry. 2002; 8(1):286-92. DOI: 10.1002/1521-3765(20020104)8:1<286::aid-chem286>3.0.co;2-d. View

15.

Zheng Y, Tong M, Zhang W, Chen X . Coexistence of spin frustration and long-range magnetic ordering in a triangular Co(II)3(mu3-OH)-based two-dimensional compound. Chem Commun (Camb). 2005; (2):165-7. DOI: 10.1039/b511612k. View

16.

Willett R, Galeriu C, Landee C, Turnbull M, Twamley B . Structure and magnetism of a spin ladder system: (C5H9NH3)2CuBr4. Inorg Chem. 2004; 43(13):3804-11. DOI: 10.1021/ic030317a. View

17.

Blackmore W, Curley S, Williams R, Vaidya S, Singleton J, Birnbaum S . Magneto-structural Correlations in Ni-Halide···Halide-Ni Chains. Inorg Chem. 2021; 61(1):141-153. PMC: 8753652. DOI: 10.1021/acs.inorgchem.1c02483. View

18.

Saines P, Bristowe N . Probing magnetic interactions in metal-organic frameworks and coordination polymers microscopically. Dalton Trans. 2018; 47(38):13257-13280. DOI: 10.1039/c8dt02411a. View

19.

Shores M, Nytko E, Bartlett B, Nocera D . A structurally perfect S = (1/2) kagomé antiferromagnet. J Am Chem Soc. 2005; 127(39):13462-3. DOI: 10.1021/ja053891p. View