Environment-sensitive emission of anionic hydrogen-bonded urea-derivative–acetate-ion complexes and their aggregation-induced emission enhancement

Anions often quench fluorescence (FL). However, strong ionic hydrogen bonding between fluorescent dyes and anion molecules has the potential to control the electronic state of FL dyes, creating new functions via non-covalent interactions. Here, we propose an approach, utilising ionic hydrogen bonding between urea groups and anions, to control the electronic states of fluorophores and develop an aggregation-induced emission enhancement (AIEE) system. The AIEE ionic hydrogen-bonded complex (IHBC) formed between 1,8-diphenylnaphthalene (p-2Urea), with aryl urea groups at the para-positions on the peri-phenyl rings, and acetate ion exhibits high environmental sensitivities in solution phases, and the FL quantum yield (QY) in ion-pair assemblies of the IHBC and tetrabutylammonium cations is more than five times higher than that of the IHBC in solution. Our versatile and simple approach for the design of AIEE dye facilitates the future development of environment-sensitive probes and solid-state emitting materials.

In addition, FT-IR spectra were measured to confirm that the acetate and urea groups formed ionic hydrogen bonds, even in the solid-state. As a result, the stretching vibration of the carbonyl of the urea group was shifted from 1651 to 1699 cm–1 upon the addition of 2 equiv of TBAAc. This result demonstrates that the urea groups of p-2Urea form intermolecular hydrogen bonds, and the C=O bond in the urea group is weakened in the solid-state without TBAAc. In addition, ionic hydrogen bonding between the N–H protons of the urea groups and acetate ion occurs with the addition of TBAAc, and the weaker intermolecular hydrogen bonds between different urea groups are eliminated with the C=O bond in the urea groups becoming stronger39. From these results, it can be concluded that p-2Urea forms an ionic hydrogen bond with acetate ion, both in DMSO and in the solid state.

Thus, we concluded that the nonlinear phenomenon caused by the addition of acetate was a result of the ionic hydrogen bonds between acetate ion and urea groups, which increased the electron-donor character of the urea group and caused intramolecular charge-transfer fluorescence and TICT fluorescence. In general, fluorophores exhibiting TICT fluorescence often display fluorescence intensity increases with increasing solvent viscosity and AIEE25. In addition, solutions with an excess of TBAAc are considered to exhibit high viscosity because the acetate anion and tetrabutylammonium cation of TBAAc experience a Coulomb force42. Therefore, we investigated the relationship between the increase in fluorescence intensity and the solvent viscosity change when adding an excess of TBAAc.In summary, we focused on urea groups, which are known to significantly change electron-donating properties by forming strong ionic hydrogen bonds with anion molecules, and investigated the optical properties of neutral fluorescent molecules and IHBCs of fluorescent urea derivatives and acetate ion in both solid-state and solution phases. These results revealed that IHBCs exhibited AIEE and high environmental sensitivities in solution phases. These interesting phenomena show the potential for the control of the characteristics of luminescent dyes by harnessing ionic hydrogen bonding interactions with molecular anions and highlight an approach for the development of solid-state light-emitting materials and environment-sensitive probes. This approach has infinite possibilities since there is an abundance of molecular anions with various structures and functions. A comprehensive investigation on superior urea architectures and molecular anions are currently in progress.