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Article

Confinement Effect of Micro- and Mesoporous Materials on the Spectroscopy and Dynamics of a Stilbene Derivative Dye

1
Departamento de Química Física, Facultad de Ciencias Ambientales y Bioquímica, and INAMOL, Universidad de Castilla-La Mancha, Avenida Carlos III, S/N, 45071 Toledo, Spain
2
Science and Engineering Faculty, Queensland University of Technology, Brisbane, QLD 4001, Australia
*
Author to whom correspondence should be addressed.
Int. J. Mol. Sci. 2019, 20(6), 1316; https://0-doi-org.brum.beds.ac.uk/10.3390/ijms20061316
Received: 8 February 2019 / Revised: 8 March 2019 / Accepted: 11 March 2019 / Published: 15 March 2019
Micro- and mesoporous silica-based materials are a class of porous supports that can encapsulate different guest molecules. The formation of these hybrid complexes can be associated with significant alteration of the physico-chemical properties of the guests. Here, we report on a photodynamical study of a push–pull molecule, trans-4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM), entrapped within faujasite-type zeolites (HY, NaX, and NaY) and MCM-41 in dichloromethane suspensions. The complex formation gives rise to caged monomers and H- and J-aggregates. Steady-state experiments show that the nanoconfinement provokes net blue shifts of both the absorption and emission spectra, which arise from preferential formation of H-aggregates concomitant with a distortion and/or protonation of the DCM structure. The photodynamics of the hybrid complexes are investigated by nano- to picosecond time-resolved emission experiments. The obtained fluorescence lifetimes are 65–99 ps and 350–400 ps for H- and J-aggregates, respectively, while those of monomers are 2.46–3.87 ns. Evidences for the presence of a charge-transfer (CT) process in trapped DCM molecules (monomers and/or aggregates) are observed. The obtained results are of interest in the interpretation of electron-transfer processes, twisting motions of analogues push–pull systems in confined media and understanding photocatalytic mechanisms using this type of host materials. View Full-Text
Keywords: H- and J-aggregates; host–guest interaction; push–pull molecule; porous silica-based materials; confinement effect H- and J-aggregates; host–guest interaction; push–pull molecule; porous silica-based materials; confinement effect
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MDPI and ACS Style

di Nunzio, M.R.; Perenlei, G.; Douhal, A. Confinement Effect of Micro- and Mesoporous Materials on the Spectroscopy and Dynamics of a Stilbene Derivative Dye. Int. J. Mol. Sci. 2019, 20, 1316. https://0-doi-org.brum.beds.ac.uk/10.3390/ijms20061316

AMA Style

di Nunzio MR, Perenlei G, Douhal A. Confinement Effect of Micro- and Mesoporous Materials on the Spectroscopy and Dynamics of a Stilbene Derivative Dye. International Journal of Molecular Sciences. 2019; 20(6):1316. https://0-doi-org.brum.beds.ac.uk/10.3390/ijms20061316

Chicago/Turabian Style

di Nunzio, Maria R., Ganchimeg Perenlei, and Abderrazzak Douhal. 2019. "Confinement Effect of Micro- and Mesoporous Materials on the Spectroscopy and Dynamics of a Stilbene Derivative Dye" International Journal of Molecular Sciences 20, no. 6: 1316. https://0-doi-org.brum.beds.ac.uk/10.3390/ijms20061316

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