Substituent Effect on AIE Mechanism of Two Coumarin Derivatives: Uncommon TICT Fluorescence in Aggregation State

Two coumarin derivatives, 7-diethylamino-3-(4-nitrophenyl)coumarin (DNC) and 7-hydroxy-3-(4-nitrophenyl)coumarin (HNC), were synthesized via Knoevenagel condensation of salicylaldehyde derivatives with 4-nitrophenylacetonitrile and then cyclization reaction. Both of them were characterized by single-crystal X-ray diffraction. The molecules of DNC are stacked via π-π interaction, while the hydrogen bond interactions instead of π-π interaction were observed in the crystal packing of HNC. Both of DNC and HNC showed solvatochromic properties and aggregation-induced emission (AIE) activities, but the AIE characteristics of them were entirely different. HNC exhibited an AIE phenomenon as the result of the restriction of twisted intramolecular charge transfer (TICT), while DNC emited peculiar dual fluorescence which was assigned to the emission based on the inhibition of TICT state formation and the emission from the TICT state respectively.

Radical Scavenging Activity and Pharmacokinetic Properties of Coumarin–Hydroxybenzohydrazide Hybrids

Free radicals often interact with vital proteins, violating their structure and inhibiting their activity. In previous studies, synthesis, characterisation, and the antioxidative properties of the five different coumarin derivatives have been investigated. In the tests of potential toxicity, all compounds exhibited low toxicity with significant antioxidative potential at the same time. In this paper, the radical scavenging activity of the abovementioned coumarin derivatives towards ten different radical species was investigated. It was found that all investigated compounds show good radical scavenging ability, with results that are in correlation with the results published in the previous study. Three additional mechanisms of radical scavenging activity were investigated. It was found that all three mechanisms are thermodynamically plausible and in competition. Interestingly, it was found that products of the Double Hydrogen Atom Transfer (DHAT) mechanism, a biradical species in triplet spin state, are in some cases more stable than singlet spin state analogues. This unexpected trend can be explained by spin delocalisation over the hydrazide bridge and phenolic part of the molecule with a low probability of spin pairing. Besides radical-scavenging activity, the pharmacokinetic and drug-likeness of the coumarin hybrids were investigated. It was found that they exhibit good membrane and skin permeability and potential interactions with P-450 enzymes. Furthermore, it was found that investigated compounds satisfy all criteria of the drug-likeness tests, suggesting they possess a good preference for being used as potential drugs.

Direct transformation of coumarins into orange-red emitting rhodols

The lactone carbonyl group of coumarin derivatives has been shown to participate in intramolecular Knoevenagel condensations, enabling the unprecedented direct transformation of coumarins into rhodols. The resulting rhodols, possessing two...