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Thermal Jahn-Teller Distortion Changes and Slow Relaxation of Magnetization in Mn(III) Schiff Base Complexes.
Chantarangkul, Chantalaksana; Patigo, Apinya; McMurtrie, John C; Clérac, Rodolphe; Rouzières, Mathieu; Gómez-Coca, Silvia; Ruiz, Eliseo; Harding, Phimphaka; Harding, David J.
Afiliación
  • Chantarangkul C; Functional Materials and Nanotechnology Centre of Excellence, Walailak University, Thasala, Nakhon Si Thammarat 80160, Thailand.
  • Patigo A; Functional Materials and Nanotechnology Centre of Excellence, Walailak University, Thasala, Nakhon Si Thammarat 80160, Thailand.
  • McMurtrie JC; Queensland University of Technology (QUT), Brisbane, Queensland 4001, Australia.
  • Clérac R; University of Bordeaux, CNRS, CRPP, UMR 5031, F-33600 Pessac, France.
  • Rouzières M; University of Bordeaux, CNRS, CRPP, UMR 5031, F-33600 Pessac, France.
  • Gómez-Coca S; Departament de Química Inorgànica i Orgànica, Institut de Recerca de Química Teòrica i Computacional, Universitat de Barcelona, Diagonal 645, 08028 Barcelona, Spain.
  • Ruiz E; Departament de Química Inorgànica i Orgànica, Institut de Recerca de Química Teòrica i Computacional, Universitat de Barcelona, Diagonal 645, 08028 Barcelona, Spain.
  • Harding P; School of Chemistry, Institute of Science, Suranaree University of Technology, Nakhon Ratchasima 30000, Thailand.
  • Harding DJ; School of Chemistry, Institute of Science, Suranaree University of Technology, Nakhon Ratchasima 30000, Thailand.
Inorg Chem ; 63(28): 12858-12869, 2024 Jul 15.
Article en En | MEDLINE | ID: mdl-38934463
ABSTRACT
The impact that the anion and alkyl group has on the electronic structures and magnetic properties of four mononuclear Mn(III) complexes is explored in [Mn(salEen-Br)2]Y (salEen-Br = 2-{[2-(ethylamino)ethylimino]methyl}-4-Br-phenol; Y = ClO4- 1 and BF4-·1/3CH2Cl2 2) and [Mn(salBzen-Br)2]Y (salBzen-Br = 2-{[2-(benzylamino)ethylimino]methyl}-4-Br-phenol; Y = ClO4- 3 and BF4- 4). X-ray structures of [Mn(salEen-Br)2]ClO4·0.45C6H14 1-hexane, [Mn(salEen-Br)2]BF4·0.33CH2Cl2·0.15C6H14 2-dcm-hexane, and 3-4 reveal that they crystallize in ambient conditions in the monoclinic P21/c space group. Lowering the temperature, 2-dcm-hexane uniquely exhibits a structural phase transition toward a monoclinic P21/n crystal structure determined at 100 K with the unit cell trebling in size. Remarkably, at room temperature, the axially elongated Jahn-Teller axis in 2-dcm-hexane is poorly defined but becomes clearer at low temperature after the phase transition. Magnetic susceptibility measurements of 1-4 reveal that only 3 and 4 show slow relaxation of magnetization with Δeff/kB = 27.9 and 20.7 K, implying that the benzyl group is important for observing single-molecule magnet (SMM) properties. Theoretical calculations demonstrate that the alkyl group subtly influences the orbital levels and therefore very likely the observed SMM properties.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Inorg Chem Año: 2024 Tipo del documento: Article País de afiliación: Tailandia Pais de publicación: Estados Unidos
Texto completo
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Inorg Chem Año: 2024 Tipo del documento: Article País de afiliación: Tailandia Pais de publicación: Estados Unidos