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Ultrafast formation of exciplex species in dicyanoanthracene ZSM-5 revealed by transient emission and vibrational spectroscopy

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Abstract

The photo-physical properties of dicyanoanthracene (DCA) molecules adsorbed on the external surface of ZSM-5 zeolite, forming DCA@ZSM-5 composites, have been investigated by picosecond transient emission, femtosecond transient absorption infrared vibrational spectroscopy, steady-state UV–vis, and quantum chemistry calculations. Following the photoexcitation at 420 nm of DCA@ZSM-5, the formation of the localized, LE, excited S1 state of DCA emitting below 500 nm is observed. LE is rapidly and quasi-exclusively converted into two distinct exciplex species, EX1 and EX2, detected by their emission above 520 nm, with a lifetime of 5 ns and 20 ns, respectively. The different transient species can be identified by the frequency of the CN stretching vibration that is a marker of the charge delocalisation and that is peaking respectively at 2162 (LE), 2174 (EX1) and 2187 (EX2) cm−1. DFT and TD-DFT calculations further support the assignment. The results show that the external surface of zeolite is an appropriate playground for the development of novel photoactive host–guest materials.

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Acknowledgements

Financial support from the Chevreul institute (FR 2638), the Ministère de l'Enseignement Supérieur et de la Recherche, the Région Haut de France, and FEDER is acknowledged. FTIR and FT Raman measurements were carried out using the facilities of the clusters of vibrational spectroscopy of the advanced characterization platform of the Institute E. Chevreul. This work was granted access to the HPC resources of CINES (Centre Informatique National de l’Enseignement Supérieur) and IDRIS (Institut du Développement et des Ressources en Informatique Scientifique) under the allocations A0090806933 and A0110806933 made by GENCI (Grand Équipement National de Calcul Intensif).

Funding

Financial support from the Chevreul institute (FR 2638), the Ministère de l'Enseignement Supérieur et de la Recherche, the Région Haut de France, and FEDER is acknowledged. FTIR and FT Raman measurements were carried out using the facilities of the clusters of vibrational spectroscopy of the advanced characterization platform of the Institute E. Chevreul. This work was granted access to the HPC resources of CINES (Centre Informatique National de l’Enseignement Supérieur) and IDRIS (Institut du Développement et des Ressources en Informatique Scientifique) under the allocations A0090806933 and A0110806933 made by GENCI (Grand Équipement National de Calcul Intensif).

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Authors and Affiliations

  1. UMR 8516, LASIRE-Laboratoire de Spectroscopie Pour Les Interactions, La Réactivité et L’Environnement, Univ. Lille, CNRS, 59000, Lille, France

    Lucie Duplouy, Matthieu Hureau, Aurélien Moncomble, Alain Moissette & Vincent De Waele

  2. Laboratoire Catalyse et Spectrochimie (LCS) ENSICAEN, UNICAEN, CNRS, Normandie Université, 6 Boulevard Maréchal Juin, 14050, Caen, France

    Svetlana Mintova

  3. UMR 8181, UCCS-Unité de Catalyse et Chimie du Solide, Univ. Lille, CNRS, Bât. C3, 59650, Villeneuve d’Ascq Cedex, France

    Olivier Gardoll

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  1. Lucie Duplouy
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Ultrafast Phenomena from attosecond to picosecond timescales: theory and experiments. Guest editors: Franck Lépine, Lionel Poisson.

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Duplouy, L., Hureau, M., Moncomble, A. et al. Ultrafast formation of exciplex species in dicyanoanthracene ZSM-5 revealed by transient emission and vibrational spectroscopy. Eur. Phys. J. Spec. Top. 232, 2145–2156 (2023). https://doi.org/10.1140/epjs/s11734-023-00813-9

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