Photoisomerization of naphthylquinolylethylenes in neutral and protonated forms

Будыка, М. Ф.; Поташова, Н. И.; Chashchikhin, Oleg V.; Гавришова, Т. Н.; Lee, V. M.

doi:10.1134/s0018143911050055

Cited by 8 publications

(6 citation statements)

References 19 publications

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“…After the absorbance of the trans (E) or cis (Z) molecule, the E -Z photoisomerization occurs generally by the well known diabatic mechanism where there is a twist around the ethylenic bond towards an energy minimum at the perpendicular configuration (pc), at about 901. 38 Thus, there exists a S 1 -S 0 internal conversion (or T 1 -S 0 intersystem crossing) followed by a relaxation to the ground state trans and cis isomers in roughly a 1 : 1 branching ratio, i.e., 1,3 E* -1,3 pc* -1 pca 1 Z + (1 À a) 1 E, where the factor a is assumed to be B0.5 in most cases. In some cases, specific structures may stabilize the S 1 state of the E geometry and increase the energy barrier to twisting 39 thus leading to fluorescence.…”

Section: Introductionmentioning

confidence: 99%

Molecular logic gates based on benzo-18-crown-6 ether of styrylquinoline: a theoretical study

Tzeli

Petsalakis

Theodorakopoulos

2016

Phys. Chem. Chem. Phys.

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In the present work, we examine the possibility of a benzo-18-crown-6 ether of styrylquinoline molecule (1) in acetonitrile solvent to act as a sensor for the Ca cation and as a molecular logical gate. DFT and TDDFT calculations are carried out using the M06-2X and the PBE0 functionals. The quinoline moiety is an electron donor and an H receptor, while the crown ether is a Ca receptor forming host-guest complexes with Ca. The calculations show that there are 8 thermally stable forms, i.e., trans and cis isomers of neutral (1), protonated (1H+), complexed with Ca (1Ca++), and both protonated and Ca complexed (1H+Ca++), with different absorption and emission spectra, and which can be interconverted from one form to another. The addition of H and/or Ca to 1 results in variation of the oscillator strength of the major absorption and emission peaks as well as in significant shifts of the major absorption and emission peaks including shifting from the vis spectral area to UV and vice versa. Consequently, 1 is a candidate for a sensor for the Ca cation. Furthermore it is shown that 1 can act as a molecular optical switch owing to its ability to be reversibly protonated and/or Ca complexed with substantial accompanying differences in the spectral properties. Similarly, 1 can be used as a sensor molecular logic gate, in which using H and Ca and irradiation as input, the emission output at 500, 470, 430, and 407 nm can be utilized as output to build AND, NOR, XOR, XNOR, INHIBIT, and IMPLICATION logic gates.

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Section: Introductionmentioning

confidence: 99%

Molecular logic gates based on benzo-18-crown-6 ether of styrylquinoline: a theoretical study

Tzeli

Petsalakis

Theodorakopoulos

2016

Phys. Chem. Chem. Phys.

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“…The study of benzene ring annelated 2SQ deriva tives, such as isomeric naphthylquinolylethylenes, showed that the quantum yield ϕ tc of these compounds is close to the theoretical limit (0.5) of the diabatic photoisomerization and does not change on passing from the neutral to the protonated form [3]. The loss of the α effect was suggested to be due to a change in shape of the PES of the S 1 state with an increase in the size of the π system from 18 electrons for 2SQ to 22 electrons for naphthylquinolylethylenes.…”

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confidence: 86%

“…These data suggest the potential energy surface (PES) of the excited state of the 2SQ cation to vary in such a way that the partition ing factor changes when the reaction follows the dia batic mechanism (the PES minimum of the S 1 state shifts towards the cis isomer relative to the PES maxi mum of the S 0 state) or the reaction proceeds partly via the adiabatic path (see [3] for detailed discussion). The property of the quantum yield ϕ tc to increase on pass ing from the neutral to the protonated form is most pronounced in the case of aza diarylethylenes (aza DAE), where the endocyclic nitrogen atom is in the α position to the double bond involved in isomerization; thus, this phenomenon can be called α effect.…”

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confidence: 99%

Spectral and photochemical properties of isomeric styrylbenzoquinolines

Будыка

Поташова

2013

High Energy Chem

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Photochemical properties of the annelated 2 styrylquinoline (2SQ) derivatives 2 styryl benzo[g]quinoline (2SBQ) and 3 styrylbenzo[f]quinoline (3SBQ) and 3 styrylacridine (3SA) have been investigated by experimental and quantum chemical methods. It has been found that the trans isomer of 3SBQ undergoes the photoisomerization reaction with a quantum yield of ϕ tc = 0.19, which increases to 0.44 for the protonated form, with the fluorescence quantum yield decreasing from 0.74 to 0.09. In contrast, the trans isomers of 2SBQ and 3SA are photochemically inert in both neutral and protonated forms, ϕ tc < 10 -3 . Quantum chemical calculation by the PM3 method show that the difference in photochemical properties of 2SBQ and 3SBQ is due to the difference in the structure of frontier molecular orbitals, which, in turn, results in the difference of the shape of the potential energy surface of excited S 1 states. Comparison of the properties of 2SBQ and 3SBQ with those of 2SQ reveals size and topological effects in the photochemistry of aza dia rylethylenes.

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“…21 Earlier, we have studied the size effect in a series of aza-DAEsderivatives of 2-styrylquinoline (SQ). Upon stepwise addition of the benzene rings to the styryl fragment, we obtained 1-(1-naphthyl)-2-(2-quinolyl)ethylene 1N2QE, 22 1-(2naphthyl)-2-(2-quinolyl)ethylene 2N2QE 22 and 1-(9-anthryl)-2-(2-quinolyl)ethylene 9A2QE 23 (Scheme 1, only s-trans and s-cis conformers relative to the vinyl-quinoline single bond are shown; depending on the structure of the aryl group, the corresponding s-trans and s-cis conformers relative to the vinyl-aryl single bond can also exist). In this series, the π-system size increases from 18 π-electrons (SQ) to 26 π-electrons (9A2QE).…”

Section: Introductionmentioning

confidence: 99%

“…An additional advantage of aza-DAEs in comparison to allcarbon analogues is that they have an extra channel for spectral tuning: under protonation, their absorption spectra are red-shifted, widening the spectral sensitivity region. 22,23 The effect of the nitrogen heteroatom on the photochemical properties of 1,2-diarylethenes has been previously studied. 25 Considering the above discussion, in the present paper, we studied the photochemical properties of 1P2QE.…”

Section: Introductionmentioning

confidence: 99%

Visible-light-driven two-way photoisomerization of 1-(1-pyrenyl)-2-(2-quinolyl)ethylene in neutral and protonated forms

Будыка

2018

Photochem Photobiol Sci

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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.

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Photoisomerization of naphthylquinolylethylenes in neutral and protonated forms

Cited by 8 publications

References 19 publications

Molecular logic gates based on benzo-18-crown-6 ether of styrylquinoline: a theoretical study

Molecular logic gates based on benzo-18-crown-6 ether of styrylquinoline: a theoretical study

Spectral and photochemical properties of isomeric styrylbenzoquinolines

Visible-light-driven two-way photoisomerization of 1-(1-pyrenyl)-2-(2-quinolyl)ethylene in neutral and protonated forms

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