Effects of Through-Bond and Through-Space Conjugations on the Photoluminescence of Small Aromatic and Aliphatic Aldimines.

Through-bond conjugation (TBC) and/or through-space conjugation (TSC) determine the photophysical properties of organic luminescent compounds. No systematic studies have been carried out to understand the transition from aromatic TBC to non-aromatic TSC on the photoluminescence of organic luminescent compounds. In this work, a series of small aromatic and aliphatic aldimines were synthesized. For the aromatic imines, surprisingly, N,1-diphenylmethanimine with the highest TBC is non-emissive, while N-benzyl-1-phenylmethanimine and N-cyclohexyl-1-phenylmethanimine emit bright fluorescence in aggregate states. The aliphatic imines are all emissive, and their maximum emission wavelength decreases while the quantum yield increases with a decrease in steric hindrance. The imines show concentration-dependent and excitation-dependent emissions. Theoretical calculations show that the TBC extents in the aromatic imines are not strong enough to induce photoluminescence in a single molecule state, while the intermolecular TSC becomes dominant for the fluorescence emissions of both aromatic and aliphatic imines in aggregate states, and the configurations and spatial conformations of the molecules in aggregate states play a key role in the formation of effective TSC. This study provides an understanding of how chemical and spatial structures affect the formation of TBC and TSC and their functions on the photoluminescence of organic luminescent materials.

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.