Huitorel, B., El Moll, H., Utrera-Melero, R., Cordier, M., Fargues, A., Garcia, A., Massuyeau, F., Martineau-Corcos, C., Fayon, F., Rakhmatullin, A., Kahlal, S., Saillard, J.-Y., Gacoin, T. & Perruchas, S. (2018) Evaluation of Ligands Effect on the Photophysical Properties of Copper Iodide Clusters. Inorganic Chemistry, 57 4328–4339.
Added by: Richard Baschera (2018-07-17 08:58:09) Last edited by: Richard Baschera (2018-07-24 13:10:29) |
Type de référence: Article DOI: 10.1021/acs.inorgchem.7b03160 Numéro d'identification (ISBN etc.): 0020-1669 Clé BibTeX: Huitorel2018 Voir tous les détails bibliographiques |
Catégories: IMN, MIOPS Créateurs: Cordier, El Moll, Fargues, Fayon, Gacoin, Garcia, Huitorel, Kahlal, Martineau-Corcos, Massuyeau, Perruchas, Rakhmatullin, Saillard, Utrera-Melero Collection: Inorganic Chemistry |
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Résumé |
Luminescent materials based on copper complexes are currently receiving increasing attention because of their rich photophysical properties, opening a wide field of applications. The copper iodide clusters formulated [Cu4I4L4] (L = ligand), are particularly relevant for the development of multifunctional materials based on their luminescence stimuli-responsive properties. In this context, controlling and modulating their photophysical properties is crucial and this can only be achieved by thorough understanding of the origin of the optical properties. We thus report here, the comparative study of a series of cubane copper iodide clusters coordinated by different phosphine ligands, with the goal of analyzing the effect of the ligands nature on the photoluminescence properties. The synthesis, structural, and photophysical characterizations along with theoretical investigations of copper iodide clusters with ligands presenting different electronic properties, are described. A method to simplify the analysis of the P-31 solid-state NMR spectra is also reported. While clusters with electron-donating groups present classical luminescence properties, the cluster bearing strong electron-withdrawing substituents exhibits original behavior demonstrating a clear influence of the ligands properties. In particular, the electron-withdrawing character induces a decrease in energy of the unoccupied molecular orbitals, that consequently impacts the emission properties. The modification of the luminescence thermochromic properties of the clusters are supported by density functional theory (DFT) calculations. This study demonstrates that the control of the luminescence properties of these compounds can be achieved through modification of the coordinated ligands, nevertheless the role of the crystal packing should not be underestimated.
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