From an antiferromagnetic insulator to a strongly correlated metal in square-lattice MCl2(pyrazine)2 coordination solids

Panagiota Perlepe; Itziar Oyarzabal; Laura Voigt; Mariusz Kubus; Daniel N. Woodruff; Sebastian E. Reyes-Lillo; Michael L. Aubrey; Philippe Négrier; Mathieu Rouzières; Fabrice Wilhelm; Andrei Rogalev; Jeffrey B. Neaton; Jeffrey R. Long; Corine Mathonière; Baptiste Vignolle; Kasper S. Pedersen; Rodolphe Clérac

doi:10.1038/s41467-022-33342-5

From an antiferromagnetic insulator to a strongly correlated metal in square-lattice MCl₂(pyrazine)₂ coordination solids

Panagiota Perlepe, Itziar Oyarzabal, Laura Voigt, Mariusz Kubus, Daniel N. Woodruff, Sebastian E. Reyes-Lillo, Michael L. Aubrey, Philippe Négrier, Mathieu Rouzières, Fabrice Wilhelm, Andrei Rogalev, Jeffrey B. Neaton, Jeffrey R. Long, Corine Mathonière, Baptiste Vignolle^*, Kasper S. Pedersen^*, Rodolphe Clérac^*

^*Corresponding author for this work

Research output: Contribution to journal › Journal article › Research › peer-review

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Abstract

Electronic synergy between metal ions and organic linkers is a key to engineering molecule-based materials with a high electrical conductivity and, ultimately, metallicity. To enhance conductivity in metal-organic solids, chemists aim to bring the electrochemical potentials of the constituent metal ions and bridging organic ligands closer in a quest to obtain metal-d and ligand-π admixed frontier bands. Herein, we demonstrate the critical role of the metal ion in tuning the electronic ground state of such materials. While VCl₂(pyrazine)₂ is an electrical insulator, TiCl₂(pyrazine)₂ displays the highest room-temperature electronic conductivity (5.3 S cm^-1) for any metal-organic solid involving octahedrally coordinated metal ions. Notably, TiCl₂(pyrazine)₂ exhibits Pauli paramagnetism consistent with the specific heat, supporting the existence of a Fermi liquid state (i.e., a correlated metal). This result widens perspectives for designing molecule-based systems with strong metal-ligand covalency and electronic correlations.

Original language	English
Article number	5766
Journal	Nature Communications
Volume	13
Issue number	1
Number of pages	7
ISSN	2041-1723
DOIs	https://doi.org/10.1038/s41467-022-33342-5
Publication status	Published - 2022

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Perlepe, P., Oyarzabal, I., Voigt, L., Kubus, M., Woodruff, D. N., Reyes-Lillo, S. E., Aubrey, M. L., Négrier, P., Rouzières, M., Wilhelm, F., Rogalev, A., Neaton, J. B., Long, J. R., Mathonière, C., Vignolle, B., Pedersen, K. S., & Clérac, R. (2022). From an antiferromagnetic insulator to a strongly correlated metal in square-lattice MCl₂(pyrazine)₂ coordination solids. Nature Communications, 13(1), Article 5766. https://doi.org/10.1038/s41467-022-33342-5

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title = "From an antiferromagnetic insulator to a strongly correlated metal in square-lattice MCl2(pyrazine)2 coordination solids",

abstract = "Electronic synergy between metal ions and organic linkers is a key to engineering molecule-based materials with a high electrical conductivity and, ultimately, metallicity. To enhance conductivity in metal-organic solids, chemists aim to bring the electrochemical potentials of the constituent metal ions and bridging organic ligands closer in a quest to obtain metal-d and ligand-π admixed frontier bands. Herein, we demonstrate the critical role of the metal ion in tuning the electronic ground state of such materials. While VCl2(pyrazine)2 is an electrical insulator, TiCl2(pyrazine)2 displays the highest room-temperature electronic conductivity (5.3 S cm-1) for any metal-organic solid involving octahedrally coordinated metal ions. Notably, TiCl2(pyrazine)2 exhibits Pauli paramagnetism consistent with the specific heat, supporting the existence of a Fermi liquid state (i.e., a correlated metal). This result widens perspectives for designing molecule-based systems with strong metal-ligand covalency and electronic correlations.",

author = "Panagiota Perlepe and Itziar Oyarzabal and Laura Voigt and Mariusz Kubus and Woodruff, {Daniel N.} and Reyes-Lillo, {Sebastian E.} and Aubrey, {Michael L.} and Philippe N{\'e}grier and Mathieu Rouzi{\`e}res and Fabrice Wilhelm and Andrei Rogalev and Neaton, {Jeffrey B.} and Long, {Jeffrey R.} and Corine Mathoni{\`e}re and Baptiste Vignolle and Pedersen, {Kasper S.} and Rodolphe Cl{\'e}rac",

year = "2022",

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Perlepe, P, Oyarzabal, I, Voigt, L, Kubus, M, Woodruff, DN, Reyes-Lillo, SE, Aubrey, ML, Négrier, P, Rouzières, M, Wilhelm, F, Rogalev, A, Neaton, JB, Long, JR, Mathonière, C, Vignolle, B, Pedersen, KS & Clérac, R 2022, 'From an antiferromagnetic insulator to a strongly correlated metal in square-lattice MCl₂(pyrazine)₂ coordination solids', Nature Communications, vol. 13, no. 1, 5766. https://doi.org/10.1038/s41467-022-33342-5

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T1 - From an antiferromagnetic insulator to a strongly correlated metal in square-lattice MCl2(pyrazine)2 coordination solids

AU - Perlepe, Panagiota

AU - Oyarzabal, Itziar

AU - Voigt, Laura

AU - Kubus, Mariusz

AU - Woodruff, Daniel N.

AU - Reyes-Lillo, Sebastian E.

AU - Aubrey, Michael L.

AU - Négrier, Philippe

AU - Rouzières, Mathieu

AU - Wilhelm, Fabrice

AU - Rogalev, Andrei

AU - Neaton, Jeffrey B.

AU - Long, Jeffrey R.

AU - Mathonière, Corine

AU - Vignolle, Baptiste

AU - Pedersen, Kasper S.

AU - Clérac, Rodolphe

PY - 2022

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N2 - Electronic synergy between metal ions and organic linkers is a key to engineering molecule-based materials with a high electrical conductivity and, ultimately, metallicity. To enhance conductivity in metal-organic solids, chemists aim to bring the electrochemical potentials of the constituent metal ions and bridging organic ligands closer in a quest to obtain metal-d and ligand-π admixed frontier bands. Herein, we demonstrate the critical role of the metal ion in tuning the electronic ground state of such materials. While VCl2(pyrazine)2 is an electrical insulator, TiCl2(pyrazine)2 displays the highest room-temperature electronic conductivity (5.3 S cm-1) for any metal-organic solid involving octahedrally coordinated metal ions. Notably, TiCl2(pyrazine)2 exhibits Pauli paramagnetism consistent with the specific heat, supporting the existence of a Fermi liquid state (i.e., a correlated metal). This result widens perspectives for designing molecule-based systems with strong metal-ligand covalency and electronic correlations.

AB - Electronic synergy between metal ions and organic linkers is a key to engineering molecule-based materials with a high electrical conductivity and, ultimately, metallicity. To enhance conductivity in metal-organic solids, chemists aim to bring the electrochemical potentials of the constituent metal ions and bridging organic ligands closer in a quest to obtain metal-d and ligand-π admixed frontier bands. Herein, we demonstrate the critical role of the metal ion in tuning the electronic ground state of such materials. While VCl2(pyrazine)2 is an electrical insulator, TiCl2(pyrazine)2 displays the highest room-temperature electronic conductivity (5.3 S cm-1) for any metal-organic solid involving octahedrally coordinated metal ions. Notably, TiCl2(pyrazine)2 exhibits Pauli paramagnetism consistent with the specific heat, supporting the existence of a Fermi liquid state (i.e., a correlated metal). This result widens perspectives for designing molecule-based systems with strong metal-ligand covalency and electronic correlations.

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