Localized Spin Dimers and Structural Distortions in the Hexagonal Perovskite Ba3CaMo2O9

Struan Simpson; Michael Milton; Sacha Fop; Gavin B. G. Stenning; Harriet Alexandra Hopper; Clemens Ritter; Abbie C. Mclaughlin

doi:10.1021/acs.inorgchem.2c01102

Localized Spin Dimers and Structural Distortions in the Hexagonal Perovskite Ba₃CaMo₂O₉

Struan Simpson, Michael Milton, Sacha Fop, Gavin B. G. Stenning, Harriet Alexandra Hopper, Clemens Ritter, Abbie C. Mclaughlin^* (Corresponding Author)

^*Corresponding author for this work

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Abstract

Extended solid-state materials based on the hexagonal perovskite framework are typified by close competition between localized magnetic interactions and quasi-molecular electronic states. Here, we report the structural and magnetic properties of the new six-layer hexagonal perovskite Ba3CaMo2O9. Neutron diffraction experiments, combined with magnetic susceptibility measurements, show that the Mo2O9 dimers retain localized character down to 5 K and adopt nonmagnetic spin-singlet ground states. This is in contrast to the recently reported Ba3SrMo2O9 analogue, in which the Mo2O9 dimers spontaneously separate into a mixture of localized and quasi-molecular ground states. Structural distortions in both Ba3CaMo2O9 and Ba3SrMo2O9 have been studied with the aid of distortion mode analyses to elucidate the coupling between the crystal lattice and electronic interactions in 6H Mo5+ hexagonal perovskites.

Original language	English
Pages (from-to)	11622-11628
Number of pages	7
Journal	Inorganic Chemistry
Volume	61
Issue number	30
Early online date	19 Jul 2022
DOIs	https://doi.org/10.1021/acs.inorgchem.2c01102
Publication status	Published - 1 Aug 2022

Bibliographical note

Notes
The authors declare no competing financial interest.

Acknowledgments
We thank the Carnegie Trust for the Universities of Scotland for a PhD Scholarship for S.S. and the U.K. Science and Technology Facilities Council (STFC) for provision of neutron beamtime at the ILL under the experiment code 5-31-2703.

Data Availability Statement

Data are available from ILL at DOI: 10.5291/ILL-DATA.5-31-2703.

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Cite this

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title = "Localized Spin Dimers and Structural Distortions in the Hexagonal Perovskite Ba3CaMo2O9",

abstract = "Extended solid-state materials based on the hexagonal perovskite framework are typified by close competition between localized magnetic interactions and quasi-molecular electronic states. Here, we report the structural and magnetic properties of the new six-layer hexagonal perovskite Ba3CaMo2O9. Neutron diffraction experiments, combined with magnetic susceptibility measurements, show that the Mo2O9 dimers retain localized character down to 5 K and adopt nonmagnetic spin-singlet ground states. This is in contrast to the recently reported Ba3SrMo2O9 analogue, in which the Mo2O9 dimers spontaneously separate into a mixture of localized and quasi-molecular ground states. Structural distortions in both Ba3CaMo2O9 and Ba3SrMo2O9 have been studied with the aid of distortion mode analyses to elucidate the coupling between the crystal lattice and electronic interactions in 6H Mo5+ hexagonal perovskites.",

author = "Struan Simpson and Michael Milton and Sacha Fop and Stenning, {Gavin B. G.} and Hopper, {Harriet Alexandra} and Clemens Ritter and Mclaughlin, {Abbie C.}",

note = "Notes The authors declare no competing financial interest. Acknowledgments We thank the Carnegie Trust for the Universities of Scotland for a PhD Scholarship for S.S. and the U.K. Science and Technology Facilities Council (STFC) for provision of neutron beamtime at the ILL under the experiment code 5-31-2703. ",

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T1 - Localized Spin Dimers and Structural Distortions in the Hexagonal Perovskite Ba3CaMo2O9

AU - Simpson, Struan

AU - Milton, Michael

AU - Fop, Sacha

AU - Stenning, Gavin B. G.

AU - Hopper, Harriet Alexandra

AU - Ritter, Clemens

AU - Mclaughlin, Abbie C.

N1 - Notes The authors declare no competing financial interest. Acknowledgments We thank the Carnegie Trust for the Universities of Scotland for a PhD Scholarship for S.S. and the U.K. Science and Technology Facilities Council (STFC) for provision of neutron beamtime at the ILL under the experiment code 5-31-2703.

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N2 - Extended solid-state materials based on the hexagonal perovskite framework are typified by close competition between localized magnetic interactions and quasi-molecular electronic states. Here, we report the structural and magnetic properties of the new six-layer hexagonal perovskite Ba3CaMo2O9. Neutron diffraction experiments, combined with magnetic susceptibility measurements, show that the Mo2O9 dimers retain localized character down to 5 K and adopt nonmagnetic spin-singlet ground states. This is in contrast to the recently reported Ba3SrMo2O9 analogue, in which the Mo2O9 dimers spontaneously separate into a mixture of localized and quasi-molecular ground states. Structural distortions in both Ba3CaMo2O9 and Ba3SrMo2O9 have been studied with the aid of distortion mode analyses to elucidate the coupling between the crystal lattice and electronic interactions in 6H Mo5+ hexagonal perovskites.

AB - Extended solid-state materials based on the hexagonal perovskite framework are typified by close competition between localized magnetic interactions and quasi-molecular electronic states. Here, we report the structural and magnetic properties of the new six-layer hexagonal perovskite Ba3CaMo2O9. Neutron diffraction experiments, combined with magnetic susceptibility measurements, show that the Mo2O9 dimers retain localized character down to 5 K and adopt nonmagnetic spin-singlet ground states. This is in contrast to the recently reported Ba3SrMo2O9 analogue, in which the Mo2O9 dimers spontaneously separate into a mixture of localized and quasi-molecular ground states. Structural distortions in both Ba3CaMo2O9 and Ba3SrMo2O9 have been studied with the aid of distortion mode analyses to elucidate the coupling between the crystal lattice and electronic interactions in 6H Mo5+ hexagonal perovskites.

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