Examinando por Autor "Aubrey, Michael L."

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    Ítem
    Electron delocalization and charge mobility as a function of reduction in a metal-organic framework
    (Nature Publishing Group, 2018-07) Aubrey, Michael L.; Wiers, Brian M.; Andrews, Sean C.; Sakurai, Tsuneaki; Reyes-Lillo, Sebastian E.; Hamed, Samia M.; Yu, Chung-Jui; Darago, Lucy E.; Mason, Jarad A.; Baeg, Jin-Ook; Grandjean, Fernande; Long, Gary J.; Seki, Shu; Neaton, Jeffrey B.; Yang, Peidong
    Conductive metal-organic frameworks are an emerging class of three-dimensional architectures with degrees of modularity, synthetic flexibility and structural predictability that are unprecedented in other porous materials. However, engendering long-range charge delocalization and establishing synthetic strategies that are broadly applicable to the diverse range of structures encountered for this class of materials remain challenging. Here, we report the synthesis of K x Fe2(BDP)3 (0 ≤ x ≤ 2; BDP2- = 1,4-benzenedipyrazolate), which exhibits full charge delocalization within the parent framework and charge mobilities comparable to technologically relevant polymers and ceramics. Through a battery of spectroscopic methods, computational techniques and single-microcrystal field-effect transistor measurements, we demonstrate that fractional reduction of Fe2(BDP)3 results in a metal-organic framework that displays a nearly 10,000-fold enhancement in conductivity along a single crystallographic axis. The attainment of such properties in a K x Fe2(BDP)3 field-effect transistor represents the realization of a general synthetic strategy for the creation of new porous conductor-based devices. © 2018 The Author(s).
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    Ítem
    From an antiferromagnetic insulator to a strongly correlated metal in square-lattice MCl2(pyrazine)2 coordination solids
    (Nature Research, 2022-12) Perlepe, Panagiota; Oyarzabal, Itziar; Voigt, Laura; Kubus, Mariusz; Woodruff, Daniel N.; Reyes-Lillo, Sebastian E.; Aubrey, Michael L.; Négrier, Philippe; Rouzières, Mathieu; Wilhelm, Fabrice; Rogalev, Andrei; Neaton, Jeffrey B.; Long, Jeffrey R.; Mathonière, Corine; Vignolle, Baptiste; Pedersen, Kasper S.; Clérac, Rodolphe
    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. © 2022, The Author(s).
  • No hay miniatura disponible
    Ítem
    From an antiferromagnetic insulator to a strongly correlated metal in square-lattice MCl2(pyrazine)2 coordination solids
    (Nature Research, 2022-12) Perlepe, Panagiota; Oyarzabal, Itziar; Voigt, Laura; Kubus, Mariusz; Woodruff, Daniel N.; Reyes Lillo, Sebastian E.; Aubrey, Michael L.; Négrier, Philippe; Rouzières, Mathieu; Wilhelm, Fabrice; Rogalev, Andrei; Neaton, Jeffrey B.; Long, Jeffrey R.; Mathonière, Corine; Vignolle, Baptiste; Pedersen, Kasper S.; Clérac, Rodolphe
    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. © 2022, The Author(s).