Topology switch between AIE and ACQ: a balance of substituents

Intermolecular interactions appearing in solution, aggregates and solid state are known to affect the photophysical properties of fluorophores, leading either to emission quenching or to emission enhancement upon aggregation. The novel strategy for the aggregation-induced fluorescence change based upon the subtle balance of the intermolecular and intramolecular charge transfer in the benzothiazole derivatives is presented here, leading to the extremely bright aggregates of the compounds dark in solution or vice versa. The introduction of the two different mild substituents into the fluorophore core results in two regioisomers exhibiting the same crystal packing, but extremely different behavior upon aggregation. Such an approach opens a simple way of controlling the AIE/ACQ behavior of small molecules in the wide range of FQY values

Tautomeric Equilibrium in 1-Benzamidoisoquinoline Derivatives

In this study, the tautomeric equilibrium of a sequence of 1-benzamidoisoquinoline derivatives was investigated with the tools of NMR spectroscopy and computational chemistry. The equilibrium between different tautomers in these systems could be controlled via the substitution effect, and the relative content of the amide form varied from 74% for the strong electron-donating NMe2 substituent to 38% for the strong electron-accepting NO2 group in the phenyl ring. In contrast to the previously investigated 2-phenacylquinoline derivatives, the most stable and thus most abundant tautomer in the 1-benzamidoisoquinoline series except the two most electron-accepting substituents was an amide. The intramolecular hydrogen bond present in the enol tautomer competed with the intermolecular hydrogen bonds created with the solvent molecules and thus was not a sufficient factor to favor this tautomer in the mixture. Although routinely computational studies of tautomeric equilibrium are performed within the continuum solvent models, it is proven here that the inclusion of the explicit solvent is mandatory in order to reproduce the experimental tendencies observed for this type of system, facilitating strong intermolecular hydrogen bonds

Chitosan as a Protective Matrix for the Squaraine Dye

Chitosan was used as a protective matrix for the photosensitive dye-squaraine (2,4-bis[4-(dimethylamino)phenyl]cyclobutane-1,3-diol). The physicochemical properties of the obtained systems, both in solution and in a solid-state, were investigated. However, it was found that diluted chitosan solutions with a few percent additions of dye show an intense fluorescence, which is suppressed in the solid-state. This is related to the morphology of the heterogeneous modified chitosan films. The important advantage of using a biopolymer matrix is the prevention of dye degradation under the influence of high energy ultraviolet (UV) radiation while the dye presence improves the chitosan heat resistance. It is caused by mutual interactions between macromolecules and dye. Owing to the protective action of chitosan, the dye release in liquid medium is limited. Chitosan solutions with a few percent additions of squaraine can be used in biomedical imaging thanks to the ability to emit light, while chitosan films can be protective coatings resistant to high temperatures and UV radiation