Spin Crossover-Assisted Modulation of Electron Transport in a Single-Crystal 3D Metal-Organic Framework
Martinez-Martinez, Ana (IMDEA Nanociencia)
Resines-Urien, Esther (IMDEA Nanociencia)
Piñeiro-López, Lucía (IMDEA Nanociencia)
Fernández-Blanco, Angel (Institut Laue-Langevin)
Mariano, Antonio Lorenzo (Université Grenoble Alpes)
Albalad Alcala, Jorge (Institut Català de Nanociència i Nanotecnologia)
Maspoch Comamala, Daniel (Institut Català de Nanociència i Nanotecnologia)
Poloni, Roberta (Université Grenoble Alpes)
Rodríguez-Velamazán, Jose Alberto (Institut Laue-Langevin)
Sañudo, E. Carolina (Universitat de Barcelona. Departament de Química Inorgànica)
Burzurí, Enrique (Universidad Autónoma de Madrid. Departamento de Física de la Materia Condensada)
Sánchez Costa, José (IMDEA Nanociencia)

Date:	2023
Abstract:	Molecule-based spin crossover (SCO) materials display likely one of the most spectacular switchable processes. The SCO involves reversible changes in their physicochemical properties (i. e. optical, magnetic, electronic, and elastic) that are coupled with the spin-state change under an external perturbation (i. e. temperature, light, magnetic field, or the inclusion/release of analytes). Although very promising for their future integration into electronic devices, most SCO compounds show two major drawbacks: (i) their intrinsic low conductance and (ii) the unclear mechanism connecting the spin-state change and the electrical conductivity. Herein, we report the controlled single-crystal-to-single-crystal temperature-induced transformation in a robust metal-organic framework, [Fe(Hbdt)]·9HO (1), being bdt = 1,4-benzeneditetrazolate, exhibiting a dynamic spin-state change concomitant with an increment in the anisotropic electrical conductance. Compound 1 remains intact during the SCO process even after approximately a 15% volume reduction. The experimental findings are rationalized by analyzing the electronic delocalization of the frontier states by means of density-functional theory calculations. The results point to a correlation between the spin-state of the iron and the electronic conductivity of the 3D structure. In addition, the reversibility of the process is proved.
Grants:	Agencia Estatal de Investigación PID2019-111479GB-I00 Ministerio de Economía y Competitividad RYC-2014-16866 Ministerio de Economía y Competitividad SEV-2016-0686 Agencia Estatal de Investigación PGC2018-098630-B-I00 Agencia Estatal de Investigación RTI2018-096075-A-C22 Agencia Estatal de Investigación RYC2019-028429-I
Rights:	Aquest material està protegit per drets d'autor i/o drets afins. Podeu utilitzar aquest material en funció del que permet la legislació de drets d'autor i drets afins d'aplicació al vostre cas. Per a d'altres usos heu d'obtenir permís del(s) titular(s) de drets.
Language:	Anglès
Document:	Article ; recerca ; Versió sotmesa a revisió
Subject:	3d metals ; Electron transport ; Metalorganic frameworks (MOFs) ; Optical- ; Physicochemical property ; Reversible change ; Spin crossover materials ; Spin crossovers ; Spin-state changes ; Switchable
Published in:	Chemistry of materials, Vol. 35, Issue 15 (August 2023) , p. 6012-6023, ISSN 1520-5002

DOI: 10.1021/acs.chemmater.3c01049

Preprint 43 p, 3.3 MB

The record appears in these collections:
Research literature > UAB research groups literature > Research Centres and Groups (research output) > Experimental sciences > Catalan Institute of Nanoscience and Nanotechnology (ICN2)
Articles > Research articles
Articles > Published articles