C3-Symmetric Luminescent Diketone with Amido-Linkage as a Polymorphic Fluorescence Emitter.

The study introduces a novel C3-symmetric ß-diketone compound, BTA-D3, and its monomeric counterpart, D, with a focus on their synthetic procedure, photophysical properties and aggregation behavior. Both compounds exhibit characteristic absorption and weak fluorescence in solution, with BTA-D3 displaying higher absorption coefficients due to its larger number of diketone units. Density Functional Theory (DFT) calculations suggest increased co-planarity of diketone groups in BTA-D3. A significant finding is the Aggregation-Induced Emission (AIE) property of BTA-D3, as its fluorescence intensity increases dramatically when exposed to specific solvent ratios. The AIE behavior is attributed to intermolecular excitonic interaction between BTA-D3 molecules in self-organized aggregates. We also studied fluorescence anisotropy of BTA-D3 and D. Despite its larger size, BTA-D3 showed reduced anisotropy values because of efficient intramolecular energy migration among three diketone units. Furthermore, BTA-D3 demonstrates unique polymorphism, yielding different emission colors and structures depending on the solvent used. A unique approach is presented for promoting the growth of self-organized aggregate structures via solvent evaporation, leading to distinct fluorescence properties. This research contributes to the understanding of C3-symmetric structural molecules and provides insights into strategies for controlling molecular alignment to achieve diverse fluorescence coloration in molecular materials.

Synthesis and Photochromic Properties of Diaryl [5]Helicene Derivatives.

Photoinduced tuning of aromaticity and correlative molecular properties has attracted enormous interest in recent years both for modulating photochromism properties and designing novel photochromic materials. Here, we report the synthesis and photochemical characterization of diaryl[5]helicene-based diarylethene molecular switches. 3,4-Bis(2,4-dimethyl-5-phenylthiophen-3-yl)dibenzo[c,g]phenanthrene derivative 1 a showed no photochromic reaction, whereas 3,4-bis(2-methyl-5-phenylthiophen-3-yl)dibenzo[c,g]phenanthrene derivative 2 a and 3,4-bis(5-methyl-2-phenylthiazol-4-yl)dibenzo[c,g]phenanthrene derivative 3 a exhibited reversible photochromism in different aprotic solvents with specific light irradiation. Meanwhile, the diarylethene compounds 2 a and 3 a underwent turn-off mode fluorescence photoswitching together with photoisomerization upon light irradiation. Remarkably, the photoinduced changes in the aromaticity of [5]helicene as a central ethene bridge along with the relative smaller activation energy and higher frequency factor facilitated the thermal bleaching rates of diarylethene switches 2 and 3 in solution. This research provides new insight for designing aromatic diarylethene photoswitches for reversible fluorescence switching, photoinduced changes in aromaticity and further fast thermal back reactions.