Triarylisocyanurate-Based Fluorescent Two-Photon Absorbers

Yohan Gautier (1) , Gilles Argouarch (1) , Floriane Malvolti (1) , Benjamin Blondeau (1) , Nicolas Richy (1) , Anissa Amar (2) , Abdou Boucekkine (1) , Krzysztof Nawara (3) , Katarzyna Chlebowicz (3) , Grażyna Orzanowska (4) , Marta Dudek (5) , Katarzyna Matczyszyn (5) , Marek Samoc (5) , Mireille Blanchard-Desce (6) , Olivier Mongin (1) , Jacek Waluk (4, 3) , Frédéric Paul (1)

1 ISCR - Institut des Sciences Chimiques de Rennes
2 UMMTO - Université Mouloud Mammeri [Tizi Ouzou]
3 UKSW - Cardinal Stefan Wyszyński University
4 Institute of Physical Chemistry [Warsaw]
5 Wroclaw University of Science and Technology
6 ISM - Institut des Sciences Moléculaires

The synthesis and characterization of six triarylisocyanurates, featuring 2,7-fluorenyl or 9,10-anthracenyl groups incorporated in their peripheral arms are reported. Photophysical studies reveal that these new octupolar derivatives are more fluorescent (Φ ≥0.60 for all new compounds except for 1,3,5-tri(9H-fluoren-2-yl)-1,3,5-triazinane-2,4,6-trione 3) and present a red-shifted lowest absorption and emission compared to their known phenyl analogues of comparable size. Depending on the nature of the terminal substituent, fast intramolecular energy transfer among the three arms or localization of the excitation on a single branch occurs after population of their first singlet excited state. The latter effect was only observed in the presence of strongly electron-releasing substituents in polar media. These new chromophores are also better two-photon absorbers than the 1,4-phenylene-based isocyanurates reported so far, with cross sections σ ≥500 GM at 770 nm for 4-NPh the fluorenyl group containing (13) and the anthracenyl group containing (14) chromophores. All these spectroscopic features, analyzed with the help of quantum chemical calculations, are crucial for the design of new biphotonic fluorescent dyes.

Mots clés: anisotropy; fluorescence; isocyanurates; nonlinear optics; two-photon absorption.

Domaines: Chimie organique

Yohan Gautier, Gilles Argouarch, Floriane Malvolti, Benjamin Blondeau, Nicolas Richy, et al.. Triarylisocyanurate-Based Fluorescent Two-Photon Absorbers. ChemPlusChem, 2020, 85 (3), pp.411-425. ⟨10.1002/cplu.202000036⟩. ⟨hal-02498788⟩