Is this how bromine spiropyran salt is converted to merocyanine under UV irradiation? A look through the prism of quantum chemical calculations.

The stability of merocyanine forms formed under UV irradiation of a solution of a spiropyran salt, in which an organic part acts as a cation and a compact bromide ion as an anion, their photophysical properties, and the formation mechanism are studied in this work using time-dependent density functional theory. Theoretical calculations show that TTC and CTT are the most stable open forms (the difference in stability energies is 10.5 and 12.0 kcal mol-1 relative to the formation energy of spiropyran, respectively). The simulated absorption bands in the UV spectrum of the merocyanine forms are observed both in the UV region at 308-366 nm and in the visible region at 544-757 nm due to n → π* and π → π* type transitions. We found that the isomerisation mechanism of spiropyran into merocyanine forms includes two key stages: the ring opening to form cisoid merocyanine forms (except unstable TCC) through conical intersection and their subsequent isomerisation to form stable transoid isomers. The length of the Cspiro-O bond is 1.97 Å and the C1'-C2'-C3'-C4' angle is 70° in the structure close to conical intersection. The stage that determines the rate of this process is the isomerisation between transoid forms, as in the case of transformation of open merocyanine forms into spiropyran.

New Triphenylphosphonium Salts of Spiropyrans: Synthesis and Photochromic Properties.

The most important area of modern pharmacology is the targeted delivery of drugs, and one of the most promising classes of chemical compounds for creating drugs of this kind are the photochromic spiropyrans, capable of light-controlled biological activity. This work is devoted to the synthesis and study of the photochromic properties of new triphenylphosphonium salts of spiropyrans. It was found that all the synthesized cationic spiropyrans have high photosensitivity, increased resistance to photodegradation and the ability for photoluminescence.

Photochromic and Luminescent Properties of a Salt of a Hybrid Molecule Based on C60 Fullerene and Spiropyran-A Promising Approach to the Creation of Anticancer Drugs.

For the first time a pyrrolidinofullerene salt containing a spiropyran group and an ammonium group, capable of reversibly reacting to UV radiation, has been synthesized. Photoinduced reactions of the synthesized compounds were studied using absorption and luminescence spectroscopies, spectral and kinetic characteristics were measured. The hybrid molecule was found to exhibit intrinsic fluorescence even in the spirocyclic form. The C60 derivative showed a higher stability and better spectral and luminescent properties than the precursor.

Synthesis, Photochromic and Luminescent Properties of Ammonium Salts of Spiropyrans.

New salts of photochromic indoline spiropyrans capable of reversibly responding to UV radiation were synthesized to develop light-controlled materials. Photoinduced reactions of the synthesized compounds were studied using absorption and luminescence spectroscopies, and the quantum yields of photoisomerization and other spectral and kinetic characteristics were measured. It was shown that the light sensitivity and photostability of the synthesized compounds are considerably influenced by the length of the spacer between the indole and ammonium nitrogen atoms.

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

Hybrid molecules based on fullerene C60 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.

Synthesis of C60 Fullerene-Quadricyclane Hybrid Compound and Its Preliminary In Vitro Antitumor Activity in Combination with Cisplatin.

This paper describes the authors' preliminary studies directed toward the possibility of the practical implementation of the idea to design efficient antitumor drugs based on hybrid molecules composed of fullerene C60 and quadricyclanes. The essence of the proposed idea is that these hybrid molecules are able to cleave DNA owing to the fullerene moiety they contain and to simultaneously thermally affect tumor cells via cleavage of the carbon-carbon bond in quadricyclanes under the action of Pd and Pt ions. As a result, testing of the cytotoxic activity in vitro for a number of fullerene C60 hybrids with the norbornadiene or quadricyclane moieties against the human T-lymphoblastic leukemia cells (Jurkat cells) in combination of the known cisplatin drug, which was taken as the source of Pt ions, showed a statistically reliable dose-dependent increase in the number of dead cells in each group, which were formed according to the amount of cisplatin added, in comparison with the control, that is, cells treated with cisplatin or quadricyclane fullerene derivatives alone. Indeed, the difference between the percentages of viable cells after treatment with either cisplatin alone or cisplatin in combination with methanofullerene 5 ranged from ∼10% (for Pt (0.015 mkM), 5 (0.015 mkM)) to ∼55% (for Pt (0.03 mkM), 5 (0.045 mkM)).

Synthesis and Properties of Energy-Rich Methanofullerenes Containing Norbornadiene and Quadricyclane Moieties.

The energy-rich methanofullerenes were synthesized for the first time by the reaction of fullerene C60 with mono- and bisquadricyclane esters of malonic acid. The C-C bond cleavage in the quadricyclane moieties of new hybrid molecules takes place in the presence of catalytic amounts of Cu, Pd, and Pt salts or complexes or SiO2 and is accompanied by heat evolution.

Aminomethylation of Fullerene C60 with N,N',N″-Triaryl- or N,N',N″-Trihetaryl-1,3,5-perhydrotriazines in the Presence of EtMgBr and Ti(Oi-Pr)4.

A new method for the functionalization of fullerenes based on the reaction between in situ generated aryl- or hetaryl-containing 1,3,5-perhydrotriazines and EtMgBr in the presence of Ti(Oi-Pr)4 has been developed. The cleavage of the triazine ring under previously developed conditions1-6 results in the formation of aminomethylated derivatives of fullerene C60 with high yields (80-90%) and selectivity (∼90%).