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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 Z - E 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. We also tested the light-stimulated ON-OFF functionality of these compounds in the presence or absence of these anions., Competing Interests: The authors declare no conflict of interest. The founding sponsors had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, and in the decision to publish the results.

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.

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. While 2-fold higher values of Stokes shift were observed for methoxy derivative, its quantum yield of fluorescence is much lower due to high nonradiative decay rate constant of the excited state., (Copyright © 2012 Elsevier B.V. All rights reserved.)