1. Surface effects on a photochromic spin-crossover iron(ii) molecular switch adsorbed on highly oriented pyrolytic graphite
- Author
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Mathieu Marchivie, Federica Bondino, M.-A. Arrio, Magdalena Milek, Giacomo Londi, Valeria Lanzilotto, Ahmad Naim, Edwige Otero, Elena Magnano, Lorenzo Poggini, Philippe Sainctavit, Amélie Juhin, Matteo Mannini, Federico Totti, Brunetto Cortigiani, Patrick Rosa, Marat M. Khusniyarov, Poggini, L., Londi, G., Milek, M., Naim, A., Lanzilotto, V., Cortigiani, B., Bondino, F., Magnano, E., Otero, E., Sainctavit, P., Arrio, M. -A., Juhin, A., Marchivie, M., Khusniyarov, M. M., Totti, F., Rosa, P., Mannini, M., Department of Chemistry 'Ugo Schiff', Università degli Studi di Firenze = University of Florence [Firenze] (UNIFI), Department of Chemistry and Pharmacy, Friedrich-Alexander Universität Erlangen-Nürnberg (FAU), Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratorio TASC (IOM CNR), Consiglio Nazionale delle Ricerche (CNR), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), We acknowledge Synchrotrons staff and Peng Chen for the help given during beamtimes. M. M. K. is grateful to the Deutsche Forschungsgemeinschaft (DFG Research Grant KH 279/3) for financial support. PR and AN acknowledge the financial support of ANR-CHIROTS (no. ANR-11-JS07-013-01), CNRS, Université de Bordeaux and Région Nouvelle Aquitaine. The research leading to these results has received funding from the European Community's Seventh Framework Programme (FP7/2007–2013) under grant agreement no. 312284. L. P., F. T. and M. M. are grateful the European Research Council through the Advanced Grant ‘MolNanoMas’ (267746). L. P. F. T and M. M. acknowledge Fondazione Ente Cassa Risparmio di Firenze (SPIN-E m project cod. 2017.0730) and MIUR-Italy ('Progetto Dipartimenti di Eccellenza 2018–2022' allocated to Department of Chemistry 'Ugo Schiff' and FIR Nanoplasmag project cod. RBFR10OAI0) for the economic support. The computing resources and the related technical support used for this work have been provided by CRESCO/ENEAGRID High Performance Computing infrastructure and its staff.57 CRESCO/ENEAGRID High Performance Computing infrastructure is funded by ENEA, the Italian National Agency for New Technologies, Energy and Sustainable Economic Development and by Italian and European research programmes, see http://www.cresco.enea.it/english for information., ANR-11-JS07-0013,CHIROTS,Synthèse, caractérisation et mesures Optiques sur composés CHIRaux à Transition de Spin(2011), European Project: 312284,EC:FP7:INFRA,FP7-INFRASTRUCTURES-2012-1,CALIPSO(2012), European Project: 67S1586(1967), Università degli Studi di Firenze = University of Florence (UniFI), and National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR)
- Subjects
Materials science ,Spin states ,02 engineering and technology ,010402 general chemistry ,Photochemistry ,01 natural sciences ,DFT ,Photochromism ,chemistry.chemical_compound ,Highly oriented pyrolytic graphite ,Diarylethene ,Spin crossover ,surface ,[CHIM.COOR]Chemical Sciences/Coordination chemistry ,General Materials Science ,Molecular switch ,Photomagnetic effect ,[CHIM.MATE]Chemical Sciences/Material chemistry ,021001 nanoscience & nanotechnology ,0104 chemical sciences ,spin-crossover iron(II) ,chemistry ,HOPG ,Sublimation (phase transition) ,0210 nano-technology - Abstract
International audience; Thin films of an iron(II) complex with a photochromic diarylethene-based ligand and featuring a spin-crossover behaviour have been grown by sublimation in ultra-high vacuum on highly oriented pyrolytic graphite and spectroscopically characterized through high-resolution X-ray and ultraviolet photoemission, as well as via X-ray absorption. Temperature-dependent studies demonstrated that the thermally induced spin-crossover is preserved at a sub-monolayer (0.7 ML) coverage. Although the photochromic ligand ad hoc integrated into the complex allows the photo-switching of the spin state of the complex at room temperature both in bulk and for a thick film on highly oriented pyrolytic graphite, this photomagnetic effect is not observed in sub-monolayer deposits. Ab initio calculations justify this behaviour as the result of specific adsorbate–substrate interactions leading to the stabilization of the photoinactive form of the diarylethene ligand over photoactive one on the surface.
- Published
- 2019