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Article Dans Une Revue Tetrahedron Chem Année : 2023

A comprehensive study of tetracyanobutadiene push-pull chromophores derived from γ-pyranylidene

Résumé

A new class of push-pull 1,1,4,4-tetracyanobutadienes (TCBDs) chromophores bearing a γ-pyranylidene as a proaromatic donor group have been developed, characterized and studied for their electrochemical, photophysical and second-order nonlinear optical (NLO) properties. [2 þ 2] Cycloaddition-retroelectrocyclizations (CA-RE) with tetracyanoethylene (TCNE) allowed the formation of new TCBDs by taking advantage of the electron-donating ability of γ-pyranylidene functional groups. The limits of the reaction between TCNE and the corresponding alkynes have been investigated, both in terms of reactivity and solubility. Electrochemical studies of pyranylidene-TCBD 1a-1j revealed two reversible reduction waves typical of TCBDs, and two oxidation waves originating from the γ-pyranylidene moiety. More complex electrochemical signals have been recorded when studying chromophores bearing multiple TCBD and/or γ-pyranylidene units. All pyranylidene-TCBDs showed panchromatic absorption properties, extending to the NIR in some cases. Changes made around the electron-withdrawing TCBD units significantly affected the ICT performance of the push-pull chromophores. Computational studies have been performed on this series of compounds to rationalize the origin of their optical properties. TD-DFT calculations confirmed that the synthesized pyranylidene-TCBDs are potential NLOphores. The second-order NLO properties of all chromophores were determined by the Electric Field-Induced Second Harmonic generation (EFISH) technique, and all systems exhibited valuable NLO properties with large μβ EFISH values for purely organic compounds, up to 5700 10 À48 esu.

Domaines

Chimie organique
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hal-04104180 , version 1 (31-05-2023)

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Paternité - Pas d'utilisation commerciale - Pas de modification

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Clotilde Philippe, Johann Melan, Alberto Barsella, Thomas Vives, Yann R Leroux, et al.. A comprehensive study of tetracyanobutadiene push-pull chromophores derived from γ-pyranylidene. Tetrahedron Chem, 2023, 5, pp.100036. ⟨10.1016/j.tchem.2023.100036⟩. ⟨hal-04104180⟩
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