Synthesis and photophysical properties of 1,1,4,4-tetracyanobutadienes derived from ynamides bearing fluorophores

Clotilde Philippe (1, 2) , Anh Thy Bui (3, 4) , Maxime Beau (1, 2) , Hugo Bloux (1, 2) , François Riobé (5, 6) , Olivier Mongin (2) , Thierry Roisnel (2) , Marie Cordier (2) , Frédéric Paul (2) , Loïc Lemiègre (1, 2) , Yann Trolez (1, 2)

1 ENSCR - Ecole Nationale Supérieure de Chimie de Rennes
2 ISCR - Institut des Sciences Chimiques de Rennes
3 UB - Université de Bordeaux
4 ISM - Institut des Sciences Moléculaires
5 UCLy - UCLy (Lyon Catholic University)
6 LC - Laboratoire de Chimie - UMR5182

1,1,4,4-Tetracyanobutadienes (TCBDs) bearing a large diversity of fluorophores were prepared following a multi-step synthesis. In a crucial last step, all compounds were obtained from the corresponding ynamides, which were particularly suitable for the formation of the TCBDs in the presence of tetracyanoethylene via a [2+2] cycloaddition/retroelectrocyclization step (CA-RE). Several fluorenyl derivatives in addition to phenanthrenyl and terphenyl ones provided ynamide-based TCBDs affording remarkable emission properties covering a large range of wavelengths. Those compounds emit both in solid state and in solution from the visible region to the NIR range, depending on the molecular structures. Quantum yields in cyclohexane reached unforeseen values for such derivatives, up to 7.8%. A huge sensitivity to the environment of the TCBDs has also been unraveled for most of the compounds since we observed a dramatic fall of the quantum yields when changing the solvent from cyclohexane to toluene, while they are almost non-emissive in dichloromethane.

Mots clés: Fluorescence; cycloaddition; tetracyanobutadiene; ynamide

Domaines: Chimie

Clotilde Philippe, Anh Thy Bui, Maxime Beau, Hugo Bloux, François Riobé, et al.. Synthesis and photophysical properties of 1,1,4,4-tetracyanobutadienes derived from ynamides bearing fluorophores. Chemistry - A European Journal, 2022, 28 (23), ⟨10.1002/chem.202200025⟩. ⟨hal-03594136⟩