RESUMEN
The untapped potential of α-carbonyl sulfoxonium ylides in epoxide ring-opening reactions has been a notable gap in current research, with such reactivity predominantly associated with the highly reactive dimethylsulfoxonium methylide. This study introduces an innovative approach wherein an epoxide indole, formed in situ from 2-hydroxyindoline-3-triethylammonium bromide, undergoes reaction with α-ester sulfoxonium ylides. The outcome is the efficient synthesis of a range of 2-hydroxyindolin-3-ylidenes, demonstrating favorable yields (41-81%) and Z/E ratios from 4:1 to those of exclusive Z isomers. Additionally, the photophysical properties of the synthesized indolinylidenes are explored, along with their derivatization using various nucleophiles under acid catalysis.
RESUMEN
This study describes the synthesis of new pyromellitic diimide (PMDI) derivatives obtained in good yields from the reaction between pyromellitic dianhydride and aminobenzazoles reactive to proton-transfer in the excited state (ESIPT). In this investigation, a non-ESIPT PMDI was also prepared for comparison. These compounds presented absorption maxima in the ultraviolet region attributed to the allowed 1π-π* electronic transitions. Redshifted absorptions were observed for the ESIPT compounds (3b-3c) due to their π-extended conjugation if compared to the non-ESIPT dye (3a). The compounds presented fluorescence emissions between 300 and 600 nm, dependent on the solvent polarity and their chemical structures. While compound 3a presents a single emission, a dual fluorescence could be observed for compounds 3b-3c. As expected for ESIPT compounds, the emission at higher energies could be related to the excited enol conformer (E*), and the emission with a large Stokes shift was attributed to the keto tautomer (K*). All compounds presented fluorescence emission in the solid state, whereas the ESIPT derivatives presented redshifted emissions with a large Stokes shift, as expected. Cyclic voltammetry was employed to investigate the electrochemical properties of these compounds. The HOMO and LUMO energy levels were estimated at -5.40 to -5.00 eV and -2.84 to -2.62 eV, and good thermal stability (Td > 150 °C) was observed. Quantum chemical calculationsusingTD-DFT and DFT were performed to investigate the electronic and photophysical features of the molecules.