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Artigo em Inglês | MEDLINE | ID: mdl-30195180


Polycyclic aromatic hydrocarbons of the general formula C6n2H6n (coronene family) were used as molecular models of graphene quantum dots (GQDs). Absorption spectra of the model compounds were calculated by ZINDO/S method. The S0 → S1 transition energy (E1) was found to decrease with n as E1 = 4.75 × n-0.633 eV. This transition is forbidden in symmetric compounds but 'switches on' upon symmetry breaking. The energy of the first bright optical peak (Ebr) was found to decrease with n as Ebr = 6.31 × n-0.6 eV. The data obtained corroborate the earlier finding that the size-independent optical properties of GQDs are determined by relatively small isolated sp2 clusters separated by sp3 (oxygen-contained) 'defects' rather than the whole (corrupted) graphene sheets; such nanoparticles actually are not quantum dots. GQDs of pure (without defects) graphene sheets with fully π-conjugated sp2 systems should exhibit size-dependent optical properties due to the quantum confinement effect.

Photochem Photobiol Sci ; 17(2): 213-220, 2018 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-29271461


Diarylethylenes with large π-systems often lose their photochemical activity (the size effect). 1-(1-Pyrenyl)-2-(2-quinolyl)ethylene (1P2QE), despite having a large conjugated π-system of 28 electrons, undergoes two-way reversible trans-cis photoisomerization both in the neutral and protonated forms with quantum yields as high as 0.13-0.83. For the neutral 1P2QE, experimental data and quantum-chemical calculations indicate a diabatic (nonadiabatic) reaction mechanism. Due to high photoisomerization quantum yields and the long-wavelength absorption band at 340-460 nm and 390-560 nm for the neutral and protonated compounds, respectively, 1P2QE can be used as a molecular photoswitch that is sensitive to visible light.

Photochem Photobiol Sci ; 16(8): 1252-1259, 2017 Aug 09.
Artigo em Inglês | MEDLINE | ID: mdl-28617494


The spectral and photochemical properties of hybrid organic-inorganic nanosystems (HNSs) were investigated. HNS consisted of CdS quantum dots (QDs) functionalized with ligands containing the isothiouronium anchor group linked by a polymethylene chain with photochromic merocyanine (MC). The HNS synthesis was carried out via a microwave-assisted one-pot technique. Energy transfer from the QDs to MC in the HNS was observed and resulted in QD fluorescence quenching and MC sensitization. Compared to the free MC, trans-cis photoisomerization of MC in the HNS was suppressed and its photodestruction was accelerated. In addition, upon HNS photolysis by visible light with energy higher than the threshold, the photosensitized destruction of the QDs (which did not absorb the applied light) occurred. The observed effects were proposed to be caused by MC adsorption on QDs surface, which leads to the restriction of the MC photoisomerization and population of the surface electron trap states of the QDs.

Chemphyschem ; 18(2): 260-264, 2017 Jan 18.
Artigo em Inglês | MEDLINE | ID: mdl-27471995


Using molecular logic gates (MLGs) for information processing attracts attention due to perspectives of creating molecular computers. Biphotochromic dyads are suitable models of photonic MLGs. However, they suffer from one weakness: the activity of one of the photochromes is often quenched because of Förster resonance energy transfer (FRET). Herein, we designed a dyad with reduced FRET, in which both photochromes keep their photoactivity thanks to spectral and spatial separation, allowing MLG switching between different states. This novel dyad reproduces the functionality of the full set of 16 two-input gates, as well a reversible gate-dual inverter, all gates are photonic.

Chemphyschem ; 13(11): 2721-8, 2012 Aug 06.
Artigo em Inglês | MEDLINE | ID: mdl-22693143


The UV (λ>305 nm) photolysis of triazide 3 in 2-methyl-tetrahydrofuran glass at 7 K selectively produces triplet mononitrene 4 (g=2.003, D(T)=0.92 cm(-1), E(T)=0 cm(-1)), quintet dinitrene 6 (g=2.003, D(Q)=0.204 cm(-1), E(Q)=0.035 cm(-1)), and septet trinitrene 8 (g=2.003, D(S)=-0.0904 cm(-1), E(S) =-0.0102 cm(-1)). After 45 min of irradiation, the major products are dinitrene 6 and trinitrene 8 in a ratio of ∼1:2, respectively. These nitrenes are formed as mixtures of rotational isomers each of which has slightly different magnetic parameters D and E. The best agreement between the line-shape spectral simulations and the experimental electron paramagnetic resonance (EPR) spectrum is obtained with the line-broadening parameters Γ(E(Q))=180 MHz for dinitrene 6 and Γ(E(S))=330 MHz for trinitrene 8. According to these line-broadening parameters, the variations of the angles Θ in rotational isomers of 6 and 8 are expected to be about ±1 and ±3°, respectively. Theoretical estimations of the magnetic parameters obtained from PBE/DZ(COSMO)//UB3LYP/6-311+G(d,p) calculations overestimate the E and D values by 1 and 8 %, respectively. Despite the large distances between the nitrene units and the extended π systems, the zero field splitting (zfs) parameters D are found to be close to those in quintet dinitrenes and septet trinitrenes, where the nitrene centers are attached to the same aryl ring. The large D values of branched septet nitrenes are due to strong negative one-center spin-spin interactions in combination with weak positive two-center spin-spin interactions, as predicted by theoretical considerations.

J Phys Chem A ; 115(30): 8419-25, 2011 Aug 04.
Artigo em Inglês | MEDLINE | ID: mdl-21682299


Photolysis of 2,6-bis(4'-azidophenyl)-4-phenylpyridine in 2-methyltetrahydrofuran (2MTHF) glass at 7 K leads to quintet 2,6-bis(4'-nitrenophenyl)-4-phenylpyridine as a mixture of rotational isomers. The electron spin resonance (ESR) spectrum of this mixture of rotamers shows a considerable broadening of many transitions in the range of 0-5000 G and cannot be reproduced by computer simulations solely based on the tuning of the spin Hamiltonian parameters g, D(Q), and E(Q) alone or on predictions of DFT calculations. The best modeling of the experimental ESR spectrum is obtained only when the large line-broadening parameter of Γ(E(Q)) = 1200 MHz along with the spin Hamiltonian g = 2.003, D(Q) = 0.154 cm(-1), and E(Q) = 0.050 cm(-1) is used in the spectral simulations. The most accurate theoretical estimations of the magnetic parameters of the dinitrene in a 2MTHF glass are obtained from the B3LYP/6-311+G(d,p)+PBE/DZ/COSMO calculations of the spin-spin coupling parameters D(SS) and E(SS). Such calculations overestimate the E(Q) and D(Q) values of the dinitrene just by 1% and 10%, respectively, demonstrating that contributions of the spin-orbit coupling parameters D(SOC) and E(SOC) to the total D(Q) and E(Q) values are negligibly small. The research shows that ESR studies of polynuclear high-spin nitrenes, obtained by photolysis of rotational isomers of the starting azides, can only be successful if large E(Q) strain effects are taken into account in the spectral simulations.

Piridinas/química , Teoria Quântica , Espectroscopia de Ressonância de Spin Eletrônica , Estrutura Molecular , Fotólise , Estereoisomerismo