Effect of a =X-NH-Fragment, (X = C, N), on / Isomerization and ON/OFF Functionality of Isatin Arylhydrazones, ((Arylamino)Methylene)Indolin-2-Ones and Their Anions.

The subject of this work was the study of thermally and photochemically stimulated « isomerization and hydrazo « azo tautomerism of and -isomers of isatin arylhydrazones and ((arylamino)methylene)indolin-2-ones and their anions. Using NMR, UV-Vis spectroscopy, kinetic measurements, and HPLC, we studied the relationship of structure, ( and isomers), of these compounds and hydrazo=azo tautomerism. The ON/OFF functionality of these compounds and their anions using light to stimulate switching between ON and OFF states was investigated.

ON/OFF Photostimulation of Isatin Bipyridyl Hydrazones: Photochemical and Spectral Study.

Four novel isatin hydrazones containing bipyridyl fragments were synthesized as potential ON/OFF switches. Hydrazone -isomers exhibit high thermal stability. The characteristic photochemical reaction for all studied hydrazones is the - isomerization in CHCl.

4-Azafluorenone and α-Carboline Fluorophores with Green and Violet/Blue Emission.

The emission properties of three 4-azafluorenone and five new α-carboline fluorophores in both solution and thin solid films were investigated. Fluorescence of the azafluorenone is clearly enhanced in thin solid films due to the presence of phenyl/biphenyl rotors, and these derivatives can be classified as green Aggregation-Induced Emission luminogens (AIEgens) with a non-emissive heteroaromatic core structure. Compared to azafluorenones, emission of α-carbolines is hypsochromically shifted to the blue region of the electromagnetic spectrum, and most of these derivatives exhibit strong violet-blue fluorescence in both solution and thin solid film layers.

Tautomeric photoswitches: anion-assisted azo/azine-to-hydrazone photochromism.

The photoswitching properties of two easily synthesized isatin 4-nitrophenylhydrazones were investigated. Although the parent isatin 4-nitrophenylhydrazones exhibit low addressability which hampers their photochromic applications, the addition of strongly basic anions to phenylhydrazone solutions creates a new Vis-Vis photochromic system with the unusual azo/azine-to-hydrazone photo-tautomerization process as the photoswitching mechanism. To the best of our knowledge, this is the first report related to the anion-assisted azo/azine-to-hydrazone photo-tautomerism.

Isatin-1,8-Naphthalimide Hydrazones: A Study of Their Sensor and ON/OFF Functionality.

Five novel hydrazones derived from substituted isatins were synthesized as potential anion sensors. Using UV-VIS, FTIR, NMR and fluorescence spectroscopy, these compounds' tautomeric equilibrium and - photoisomerization were studied in DMF and CHCl₃, depending on the hydrazone concentrations, the presence of basic anions and light stimulation. Anion recognition aspects (PF₆, HSO₄, Br, Cl, NO₃, F and CH₃COO) and these receptors' detection limits were also studied.

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.

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.

3-(7-Dimethylamino)coumarin N-phenylsemicarbazones in solution and polymer matrices: Tuning their fluorescence via para-phenyl substitution.

The photo-physical properties of five new para-phenyl substituted derivatives of 3-(7-dimethylamino)coumarin N-phenylsemicarbazone with various electron-withdrawing substituents R (RF, Br, CF3, CN or NO2) in the para-position on the phenyl ring were investigated in solvents and in polymer matrices. Tuning their fluorescent properties via para-substitution is discussed in terms of Twisted Intra-molecular Charge-Transfer (TICT) state formation, specific solute-solvent interactions (hydrogen bonding), fluorescent H-aggregates formation, and the solvent polarity and polymer matrix effects.

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.

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.

A study on the alkaline hydrolysis of isatin-β-thiosemicarbazone by capillary electrophoresis with enhanced sample loadability.

An analytical potential of capillary zone electrophoresis (CZE) with enhanced sample loadability (a 200nL injection volume) in determination of alkaline hydrolysis products of isatin-β-thiosemicarbazone (IBT), a compound with important biological activity, has been studied. The CZE separation conditions for a complete resolution of transformation products, i.e.

Spectral properties of substituted coumarins in solution and polymer matrices.

The absorption and fluorescence spectra of substituted coumarins (2-oxo-2H-chromenes) were investigated in solvents and in polymer matrices. The substitutions involved were: (1) by groups with varying electron donating ability such as CH₃, OCH₃ and N(CH₃)₂, mainly, but not exclusively, in positions 7 and (2), by either CHO or 4-PhNHCONHN=CH- in position 3. While the spectra of non-substituted coumarin-3-carbaldehyde has absorptions at approximately 305 and 350 nm, substitution at position 7 leads to remarkable changes in the shape of the absorption spectrum and shifts the absorption to a longer wavelength.

Spectral properties of binaphthalene-coumarins interconnected through hydrazone linkage.

Photophysical properties of new coumarin-3-carbaldehyde (dihydrodinaphtho[2,1-c:1',2'-e]azepin-N-yl)imines bearing dimethylamino and methoxy groups at position 7 of coumarin were investigated. Dimethylamino derivative exhibits different solvent polarity dependence of fluorescent characteristics for nonpolar, medium polar and highly polar solvents. This effect can be rationalized by diverse charge distribution in the singlet excited state due to its different stabilization by solvation in the solvents of particular group.

Influence of polarity of solvents on the spectral properties of bichromophoric coumarins.

Absorption and fluorescence spectra of bichromophoric coumarins were investigated in different solvents and in polymer matrices. These bichromophoric coumarins were composed of a coumarin dimethylamino-substituted at position 7 or unsubstituted coumarin and phthalimide or a 1,8-naphthylimide linked with an iminomethyl bridge to the position 3 or 8 of the coumarin ring. Absorption spectra of 7-dimethylamino derivatives in position 3 of coumarin were quite similar, exhibiting broad bands around 430-440 nm like the parent compound 7-dimethylaminocoumarin-3-carbaldehyde.

Photophysical properties and photostability of novel benzothiazole-based D-π-A-π-D systems.

The photophysical properties and photochemical stability of two novel D-π-A-π-D systems based on a benzothiazole core and terminal N,N-dimethylaminophenyl and N,N-diphenylaminophenyl groups were investigated. The quantum yield of photoreactions (Φ) was determined for various oxygen concentrations in the solvent (CH2Cl2) and various irradiation wavelengths. Trans-cis photoisomerization is proposed as a photobleaching mechanism during irradiation at longer wavelength due to charge-transfer transitions.

Synthesis and study of novel coumarin derivatives potentially utilizable as memory media.

Novel coumarin derivatives, 2-oxo-2H-chromenecarbaldehyde hydrazones were prepared by reaction of substituted 2-oxo-2H-chromenecarbaldehydes with N-aminoimides in ethanol in the presence of 4-toluenesulfonic acid as catalyst. The photochromic and thermochromic properties of the prepared compounds were investigated.

Synthesis and photochemistry of 1-iodocyclohexene: influence of ultrasound on ionic vs. radical behaviour.

Simultaneous application of UV light and ultrasonic irradiation to a reaction mixture containing 1-iodocyclohexene is reported. The irradiation of 1-iodocyclohexene in methanol was carried out with or without addition of zinc. The effect of ultrasound or mechanical stirring on this solid-liquid system was also compared.

Spectroscopic study of 2-[2-(4-cyclaminophenyl)ethen-1-yl] benzothiazoles and their N-allylbenzothiazolium bromides. Solvent and substituent effects on their ultraviolet-visible and fluorescence spectra.

UV-vis and fluorescence spectra of 2-[2-(4-cyclaminophenyl)ethen-1-yl] benzothiazoles 1 and their N-allylbenzothiazolium bromides 2 have been measured and interpreted. The substitution and solvent effects on electronic structure and spectra have been investigated. The benzothiazolium salts substituted with saturated cyclamines show strong push-pull character and can be used as potential NLO materials.