Developing Quinoidal Fluorophores with Unusually Strong Red/Near-Infrared Emission

Despite the dominant position of aromatic fluorophores, we report herein the design and synthesis of quinoidal fluorophores based on rarely emissive quinoidal bithiophene. Quinoidal bitheno­[3,4-b]­thiophene, QBTT-C6, consisting of cruciform-fused (E)-1,2-bis­(5-hexylthiophen-2-yl)­ethene and quinoidal bithiophene, shows a fluorescence quantum yield of 8.5%, 25-fold higher than that of the parent quinoidal QBT chromophore, but its maximum emission is at similar wavelengths. QBTT-Ar’s featuring intramolecular charge transfer can further shift the maximum emission into the near-infrared region. The intramolecular charge transfer is programmably enhanced by tuning the substituents on the aryl groups from the electron-withdrawing trifluoromethyl to the electron-donating methoxy groups. Unexpectedly, a positive relationship between intramolecular charge transfer and fluorescence quantum yield is observed; as a result, QBTT-FL gives an unprecedentedly high fluorescence quantum yield of up to 53.1% for quinoidal oligothiophenes. With detailed photophysical and theoretical investigations, we demonstrate that the nonradiative intersystem crossing (S1 → T2) is significantly restrained in QBTT-Ar’s, which can be attributed to the faster reverse intersystem crossing (T2 → S1) characteristic of a small activation energy. This work reveals the possibility for developing red/near-infrared fluorophores from the less explored quinoidal molecules because of their intrinsically narrow bandgaps.