Molecular Conformation Engineering To Achieve Longer and Brighter Deep Red/Near-Infrared Emission in Crystalline...

A series of molecules 1-5 containing the same fluorophore and different alkyl chains are synthesized to reveal the significant effect of molecular conformations on the emission properties. In crystalline state, molecules 1-3 exhibit strong orange emissions with maxima (λ_em) of about 600 nm and quantum yields (Φ_F) of around 60%, while molecules 4 and 5 display much longer emissions to the deep red/near-infrared (NIR) region as well as even higher efficiencies (λ_em = 693 nm, Φ_F = 73% for 4; λ_em = 654 nm, Φ_F = 93% for 5). The largely red-shifted emissions of 4 and 5 as well as the significantly improved Φ_F are very unusual. Furthermore, the Φ_F of 4 and 5 represent the highest values among organic solids with similar deep red/NIR emission wavelengths. On the basis of the experimental measurements and theoretical calculations, the new molecular design of conformation engineering, the impressive emission properties, and the potential NIR fluorescence sensing and lasing applications are comprehensively investigated.