Excited State Proton Transfers in Hybrid Compound Based on Indoline Spiropyran of the Coumarin Type and Azomethinocoumarin in the Presence of Metal Ions.

Spectral-luminescence properties of a hybrid compound containing a coumarin-type spiropyran and an azomethinocoumarin fragment in toluene-acetonitrile solution in the presence of Li, Ca, Zn and Mg ions are reported. Two excited state proton transfers can occur in the hybrid compound-the transfer of a proton from the OH group of the 7-hydroxy coumarin tautomer to the N atom of the C=N bond of the azomethine fragment leading to green ESIPT fluorescence with a maximum at 540 nm and from the OH group of the 7-hydroxy coumarin tautomer to the carbonyl group of the pyrone chromophore, which leads to the formation of the 2-hydroxyl-tautomer of coumarin with blue fluorescence with a maximum at 475 nm. Dependence of these excited state proton transfers on the metal nature and irradiation with an external UV source is discussed.

Hybrid Molecules Based on Fullerene C60 and Dithienylethenes. Synthesis and Photochromic Properties. Optically Controlled Organic Field-Effect Transistors.

Hybrid molecules based on fullerene C and dithienylethene and its perfluorinated analog not inferior in the efficiency of phototransformations to the initial photochromic compounds were synthesized for the first time. The resulting pyrrolidinofullerenes containing photochromic moieties were used to fabricate organic field-effect transistors (OFETs) with output and transfer characteristics ten times exceeding similar characteristics of devices based on staring dithienylethenes. It was found that OFETs based on hybrid molecules with dithienylethenes are four times less efficient than devices based on hybrid molecules with perfluorinated analogs.

Photochromic systems with photoinduced emission modulation of colloidal CdSe quantum wells.

A spectroscopic study of photochromic systems containing two-dimensional CdSe nanoparticles (colloidal quantum wells) and photochromic compounds of the thermally relaxing chromene and thermally irreversible diarylethene classes in solutions was carried out. First, the systems were found to exhibit modulation of emission of two-dimensional nanoparticles in accordance with the photochromic transformations of compounds due to Förster resonance energy transfer (FRET) from the two-dimensional nanoparticles to photoinduced photochromic isomers.

Photochromic and luminescence properties of a hybrid compound based on indoline spiropyran of the coumarin type and azomethinocoumarin.

A novel hybrid compound whose molecule includes the photochromic spiropyran fragment and two fluorophores - coumarin and salicylideneimine - was synthesized by the reaction of two equivalents of 8-formyl-7-hydroxy-4-methylcoumarin with 5-amino-1,3,3-trimethyl-2-methyleneindoline. Its spectral-kinetic and fluorescence properties were studied in comparison with model compounds - 7-hydroxy-4-methyl-coumarin, spiropyran of the coumarin type, and azomethinocoumarin in toluene and ethanol. It was shown that the hybrid compound exhibited photochromic transformations in both solvents.

Inheritance of Photochromic Properties of Nitro-Substituted and Halogenated Spiropyrans Containing the Pyrrolidino[60]fullerene.

The photophysical and isomerization properties of hybrid molecular compounds that consist of photochromic nitro-substituted and halogenated spiropyran derivatives bonded to the surface of the [60]fullerene cage through the pyrrolidine bridge were investigated using various functionals and basis sets of TD-DFT and semiempirical quantum-chemical approaches. The role of nπ* states formed by the lone pairs of substituents in changing of the electronic structure and photochromic properties of spiropyran derivatives was evaluated. The S(spiropyran) → intermediate nπ* states → S(merocyanine) channel for phototransformation of the hybrid compound containing a nitro-substituted spiropyran moiety was established and compared with similar systems of halogenated spiropyrans attached to the [60]fullerene bulk where photoinduced isomerization does not process due to high probability of internal conversion from the excited electronic state localized on the spiropyran fragment to the states of the pyrrolidino[60]fullerene.

Synthesis and characterization of nonsymmetric cyclopentene-based dithienylethenes.

Nonsymmetric cyclopentene-based dithienylethenes, containing both thienyl and benzothienyl units, have been synthesized for the first time, employing intramolecular McMurry reaction as a key transformation to target compounds 10 and 16. Photochromic properties of these compounds were examined in toluene and acetonitrile solutions, PMMA layers, solid films, and crystal phase. To explain an unprecedented single-crystalline photochromism phenomena of 10, X-ray crystallographic analysis was performed, revealing a significant influence of strong S···S interatomic interactions on the intramolecular distance between two photochemical reaction centers in the molecule.

Coumarinyl(thienyl)thiazoles: novel photochromes with modulated fluorescence.

Novel photochromic 5-(3'-coumarinyl)-4-(3''-thienyl)thiazoles have been synthesized. These compounds display intensive fluorescence emission in the open form A, which is modulated by light. Fluorescence intensity decreases significantly upon irradiation of A with UV-light (lambda<400 nm) due to formation of the cyclic form B.