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.
The photochemical properties of two basic easily synthesized isatin N(2)-phenylhydrazones were investigated. Contrary to the corresponding isatin N(2)-diphenylhydrazones, only Z-isomers were isolated from the reaction mixtures during the synthesis due to their stabilization by intramolecular hydrogen bonding. Although the presence of the C=N double bond creates conditions for the formation of a simple on-off photoswitch, the low photochemical quantum yield and particularly the low switching amplitude in absorbance hamper their photochromic applications. However, the addition of strongly basic anions to phenylhydrazone solutions leads to isatin NH group deprotonation and creates a new diazene T-type Vis-Vis photochromic system with sufficiently separated absorption maxima. Interestingly, although the thermally stable A-form is also photostable in ambient light, its irradiation with a stronger LED source leads to thermally unstable B-form formation which rapidly isomerizes back to the corresponding A-form. The process is reversible and switching cycles can be repeated in both directions. The important advantages of this two-component organic chromophore-inorganic anion photochromic system are its easy synthesis, easy handling due to its insensitivity to room light, easy further structural modification and reversibility. The corresponding photochemical quantum yield, however, remains relatively low (Φ ∼ 0.001). The theoretically calculated properties are in agreement with the obtained experimental results and support the proposed reaction mechanism.
Easily synthesized and highly efficient F− and CH3COO− anion sensors based on reversible keto (hydrazo)/enolate (azo) acid–base equilibrium followed by interesting conformational change in solution.
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.
The self-association and tautomerism of (E)-isatin-3-4-phenyl(semicarbazone) Ia and (E)-N-methylisatin-3-4-phenyl (semicarbazone) IIa were investigated in solvents of various polarity. In weakly interacting non-polar solvents, such as CHCl 3 and benzene, phenylsemicarbazone concentrations above 1×10 À5 mol dm À3 result in the formation of dimers or higher aggregates of E-isomers Ia and IIa. This aggregate formation prevents room temperature E-Z isomerization of la and IIa to more stable Z-isomers. In contrast to the situation in non-polar solvents, E-Z isomerization from the monomeric form of phenylsemicarbazone Ia and IIa E-isomers occurs in highly interactive polar solvents including MeOH and DMF only at temperatures above 70°C. Moreover, decrease in phenylsemicarbazone concentration below 1×10 À4 mol dm À3 in these highly solute-solvent interacting systems leads to aggregate dissociation, and a new hydrazonol tautomeric form with a high degree of conjugation predominates in these solutions. Theoretical calculations confirm obtained experimental results.
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