The magnetic properties of MAl4(OH)12SO4·3H2O with M = Co2+, Ni2+, and Cu2+ determined by a combined experimental and computational approach
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The magnetic properties of the nickelalumite-type layered double hydroxides (LDH), MAl4(OH)12(SO4)·3H2O (MAl4-LDH) with M = Co2+ (S = 3/2), Ni2+ (S = 1), or Cu2+ (S = 1/2) were determined by a combined experimental and computational approach. They represent three new inorganic, low-dimensional magnetic systems with a defect-free, structurally ordered magnetic lattice. They exhibit no sign of magnetic ordering down to 2 K in contrast to conventional hydrotalcite LDH. Detailed insight into the complex interplay between the choice of magnetic ion (M2+) and magnetic properties was obtained by a combination of magnetic susceptibility, heat capacity, neutron scattering, solid-state NMR spectroscopy, and first-principles calculations. The NiAl4- and especially CoAl4-LDH have pronounced zero-field splitting (ZFS, easy-axis and easy-plane, respectively) and weak ferromagnetic nearest-neighbour interactions. Thus, they are rare examples of predominantly zero-dimensional spin systems in dense, inorganic matrices. In contrast, CuAl4-LDH (S = 1/2) consists of weakly ferromagnetic S = 1/2 spin chains. For all three MAl4-LDH, good agreement is found between the experimental magnetic parameters (J, D, g) and first-principles quantum chemical calculations, which also predict that the interchain couplings are extremely weak (< 0.1 cm−1). Thus, our approach will be valuable for evaluation and prediction of magnetic properties in other inorganic materials.
| Originalsprog | Engelsk |
|---|---|
| Tidsskrift | Physical Chemistry Chemical Physics |
| Vol/bind | 25 |
| Udgave nummer | 4 |
| Sider (fra-til) | 3309–3322 |
| Antal sider | 14 |
| ISSN | 1463-9076 |
| DOI | |
| Status | Udgivet - 2023 |
Bibliografisk note
Funding Information:
Mr Nicolai D. Skjold is thanked for synthesis of the D-NiAl-LDH sample. Prof. Hans J. Aa. Jensen and Assoc. Prof. Erik Donovan Hedegaard are thanked for valuable discussions. This work was funded by the Danish Council for Independent Research Science and Universe (grant DFF-7014-00198), the Danish National Committee for Research Infrastructure through the instrument centre DANSCATT, the Academy of Finland (grant 331008), the Austrian science fund (FWF, grant P28724), and University of Oulu (Kvantum Institute). This work is partly based on experiments performed at the Swiss spallation neutron source SINQ, Paul Scherrer Institute, Villigen, Switzerland. HJ was funded by the EU Horizon 2020 program under the Marie Sklodowska-Curie grant agreement No. 701647 and the Carlsberg Foundation. Computations were carried out with resources from CSC-the Finnish IT Centre for Science and the Finnish Grid and Cloud Infrastructure project (persistent identifier urn:nbn:fi:research-infras-2016072533). 4
Funding Information:
Mr Nicolai D. Skjold is thanked for synthesis of the D-NiAl4-LDH sample. Prof. Hans J. Aa. Jensen and Assoc. Prof. Erik Donovan Hedegaard are thanked for valuable discussions. This work was funded by the Danish Council for Independent Research Science and Universe (grant DFF-7014-00198), the Danish National Committee for Research Infrastructure through the instrument centre DANSCATT, the Academy of Finland (grant 331008), the Austrian science fund (FWF, grant P28724), and University of Oulu (Kvantum Institute). This work is partly based on experiments performed at the Swiss spallation neutron source SINQ, Paul Scherrer Institute, Villigen, Switzerland. HJ was funded by the EU Horizon 2020 program under the Marie Sklodowska-Curie grant agreement No. 701647 and the Carlsberg Foundation. Computations were carried out with resources from CSC-the Finnish IT Centre for Science and the Finnish Grid and Cloud Infrastructure project (persistent identifier urn:nbn:fi:research-infras-2016072533).
Publisher Copyright:
© 2023 The Royal Society of Chemistry.
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