Dramatically Enhanced and Red-shifted Photoluminescence Achieved by Introducing an Electron-withdrawing Group into a Non-traditional Luminescent Small Organic Compound

Small organic compounds without any traditional fluorescent chromophores are generally non-emissive, and only very few are reported to emit weak blue fluorescence. Here we synthesized a non-traditional luminescent small organic compound N-(2,2,2-trifluoroethyl)acrylamide (TFAM) with dramatically enhanced and red-shifted photoluminescence by introducing a strong electron-withdrawing group into acrylamide (AM). Very impressively, TFAM emits cyan (472 nm) and yellow-green (560 nm) fluorescence in solutions and solid state, respectively. TFAM also shows aggregation-induced emission enhancement (AIEE) and excitation-dependent fluorescence (EDF) characteristics, as well as temperature and metal cations-responsive fluorescence. Theoretical calculations show that the introduction of electron-withdrawing group leads to a lower energy gap between the HOMO–LUMO energy levels in TFAM than in AM. And strong cooperative hydrogen bonds are formed in TFAM molecules, resulting in rigidification of molecular conformations. The study provides a strategy for preparing non-traditional luminescent compounds with enhanced and red-shifted photoluminescence.