7-Dialkylaminocoumarin Oximates: Small Molecule Fluorescent "Turn-On" Chemosensors for Low-Level Water Content in Aprotic Organic Solvents.

The water sensing properties of two efficient two-component fluorescent "turn-on" chemo-sensors based on the 7-dialkylaminocoumarin oxime acid-base equilibrium were investigated. Interestingly, although simple frontier orbital analysis predicts an intramolecular photoinduced electron transfer quenching pathway in conjugated oximates, TD-DFT (Time-dependent density functional theory) quantum chemical calculations support non-radiative dark S1 excited state deactivation as a fluorescence quenching mechanism. Due to the acid-base sensing mechanism and sensitive "turn-on" fluorescent response, both studied coumarin aldoxime chemosensors exhibit rapid response to low-level water content in polar aprotic solvents, with detection limits comparable to chemodosimeters or chemosensors based on interpolymer π-stacking aggregation.

Effect of Structure on Charge Distribution in the Isatin Anions in Aprotic Environment: Spectral Study.

Five isatin anions were prepared by deprotonation of initial isatins in aprotic solvents using basic fluoride and acetate anions (F- and CH3COO-). The F- basicity is sufficient to deprotonate isatin NH hydrogen from all the studied compounds. This process is reversible. In the presence of proton donor solvents, the anions form the corresponding isatins. The isatin hydrogen acidity depends on the overall structure of the isatin derivatives. The anions were characterized by ultraviolet-visible (UV-Vis), Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopy. Interestingly, the anions form aggregates at concentrations above 10-3 mol·dm-3. Further, the effect of cations on the UV-Vis spectra of the studied anions was studied. Charge transfer and its distribution in the anion depends on the radius and the cation electron configuration. The alkali metal cations, tetrabutylammonium (TBA⁺), Mg2+ and Ag⁺, interact with the C-2 carbonyl oxygen of the isatin anion. The interaction has a coulombic character. On the other hand, Cd2+, Zn2+, Hg2+, Co2+, and Cu⁺ cations form a coordinate bond with the isatin nitrogen.

7-(Dimethylamino)coumarin-3-carbaldehyde and its phenylsemicarbazone: TICT excited state modulation, fluorescent H-aggregates, and preferential solvation.

The photophysical properties of 7-(dimethylamino)coumarin-3-carbaldehyde 3 and its phenylsemicarbazone 4 were investigated in solvents of various polarity and in differing solvent mixtures. The different fluorescent quantum yield (ΦF) behavior of 3 and 4 in highly polar solvents is discussed in terms of Twisted Intramolecular Charge-Tranfer (TICT) state formation and the specific solute-solvent interactions. Because of the weak intermolecular hydrogen bonding ability of both the radiative ICT and nonradiative TICT excited state of 3 and the linear steep decrease in ΦF from a medium to high polarity region, coumarin 3 could be a useful polarity probe for microenvironments containing hydrogen bonding groups. Compared to 3, coumarin 4 exhibits the highest ΦF values in highly polar solvents with strong hydrogen bond acceptor ability. The high quantum yield of fluorescence in DMSO, DMF, and alcohols qualifies coumarin 4 as a laser dye in the given medium, with kF higher than k(nr). Contrary to previous reports that many H-aggregates are nonfluorescent in nature, coumarin 3 forms highly fluorescent H-aggregates in MeOH and EtOH. On the basis of the restrictions of the Kasha-exciton theory model, we assume that the formation of fluorescent H-dimer aggregates of 3 is driven by π(+)-π(-) interactions. To the best of our knowledge, this is the first report on aggregation of coumarin dye in alcoholic solutions. In addition, restrictions in the fitting procedure relating to determination of the solvation number, n, using the Covington-Newman model of preferential solvation and also the solvent nonideality parameter, h', are discussed in this article.

Isatinphenylsemicarbazones as efficient colorimetric sensors for fluoride and acetate anions - anions induce tautomerism.

The anion induced tautomerism of isatin-3-4-phenyl(semicarbazone) derivatives is studied herein. The interaction of F(-), AcO(-), H2PO4(-), Br(-) or HSO4(-) anions with E and Z isomers of isatin-3-4-phenyl(semicarbazone) and N-methylisatin-3-4-phenyl(semicarbazone) as sensors influences the tautomeric equilibrium of these sensors in the liquid phase. This tautomeric equilibrium is affected by (1) the inter- and intra-molecular interactions' modulation of isatinphenylsemicarbazone molecules due to the anion induced change in the solvation shell of receptor molecules and (2) the sensor-anion interaction with the urea hydrogens. The acid-base properties of anions and the difference in sensor structure influence the equilibrium ratio of the individual tautomeric forms. Here, the tautomeric equilibrium changes were indicated by "naked-eye" experiment, UV-VIS spectral and (1)H NMR titration, resulting in confirmation that appropriate selection of experimental conditions leads to a high degree of sensor selectivity for some investigated anions. Sensors' E and Z isomers differ in sensitivity, selectivity and sensing mechanism. Detection of F(-) or CH3COO(-) anions at high weakly basic anions' excess is possible.