Intramolecular cyclization of β-nitroso-o-quinone methides. A theoretical endoscopy of a potentially useful innate ‘reclusive’ reaction

Tzeli, Demeter; Tsoungas, Petros G.; Petsalakis, Ioannis D.; Kozielewicz, Paweł; Zloh, Mire

doi:10.1016/j.tet.2014.11.020

Cited by 18 publications

(37 citation statements)

References 86 publications

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“…For PET systems, geometry optimization of the excited state is required in order to reach the emission geometry, which is often very difficult to achieve due to interactions with other close‐lying excited electronic states. Furthermore, the effect of the environment, such as the solvent, needs to be accounted for: state‐specific treatment of the solvent is required for the excited states while explicit inclusion of solvent molecules in addition to the implicit methods might be necessary …”

Section: Introductionmentioning

confidence: 98%

Theoretical study of the photophysical processes of a styryl‐bodipy derivative eliciting an AND molecular logic gate response

Tzeli

Petsalakis

Theodorakopoulos

2019

Int J of Quantum Chemistry

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We study, via density functional theory and time dependent DFT calculations, the photophysical processes of a styryl‐bodipy derivative, which acts as a three metal‐cation‐receptor fluorophore in order to (a) gain information on the appropriate computational approach for successful prediction of molecular logic gate candidates, (b) rationalize the available experimental data and (c) understand how the given combination of three different receptors with the BODIPY fluorophore presents such interesting optoelectronic responses. The fluorophore (1), its monometallic complexes (1‐Ca 2+, 1‐Zn 2+, and 1‐Hg 2+), and its trimetallic complex (2) are studied. The calculated λmax values for absorption and emission are in excellent agreement with experimental data. It was found that the observed quenching of emission of 1 and of the monometallic complexes is attributed to the fact that their first excited state is a charge‐transfer state whereas this does not happen for the complex 2. It should be noted that for the correct ordering of the excited states, the inclusion of corrections to the excitation energies for nonequilibrium solvent effects is required; while in the case of 1‐Ca 2+, the additional explicit inclusion of the solvent is necessary for the quenching of the emission spectra.

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Section: Introductionmentioning

confidence: 98%

Theoretical study of the photophysical processes of a styryl‐bodipy derivative eliciting an AND molecular logic gate response

Tzeli

Petsalakis

Theodorakopoulos

2019

Int J of Quantum Chemistry

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“…The water molecules were added because (a) the M 2+ cations can be coordinated with the solvent and (b) we wanted to include the solvent both explicitly and implicitly in the present calculations since it has been established that the augmentation of implicit solvent calculations with molecules of solvent is required in some cases, see for instance refs. [,]. Here, the inclusion of coordinating solvent molecules explicitly has been done in accordance with the usual coordination number for each cation.…”

Section: Methodsmentioning

confidence: 99%

The solvent effect on a styryl‐bodipy derivative functioning as an AND molecular logic gate

Tzeli

Petsalakis

Theodorakopoulos

2020

Int J of Quantum Chemistry

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We study via DFT and TDDFT calculations the photophysical processes of a styrylbodipy derivative, (1), of its monometallic complexes 1-M 2+ (M = Ca, Zn, and Hg), and its trimetallic complex (2) unprotonated, protonated and complexed with water molecules in water solvent and in acidic conditions. The main targets of this study are to gain information regarding published reports on fluorophore species mentioning that fluorescent switching results from trace water, to study how 1 behaves in water solvent which is a common used solvent for molecular logic gates (MLG), and how it behaves in acidic conditions. We conclude that in water solvent, as in acetonitrile solvent (which was found before both theoretically and experimentally) there will be a quenching of emission spectra in 1 and 1-M 2+ and a retaining of emission in 2. However, contrary to acetonitrile solvent, in water, a weak peak will be observed for 1 and 1-M 2+ , due to a small ratio of reversible protonation, showing that in acetonitrile 1 acts as a better MLG candidate than in water solvent. On the other hand, in acidic conditions all five species will emit and as a result, 1 will not be an AND MLG, showing that the selection of the solvent conditions is crucial for a species to act as an MLG candidate. Finally, we conclude that the retaining of emission is accomplished by the simultaneous tetrahedral geometry of all three aniline N atoms.charge-transfer, DFT calculations, molecular logic gate, spectra, styryl-bodipy | INTRODUCTIONFluorescence chemosensors and molecular switches present applications in diverse sciences, such as chemistry, electronics, materials, and medicine. [1][2][3][4] Molecules respond to changes in their environment, such as changes of pH, temperature, solvent, viscosity, the presence of various ions, of neutral species, and so on. [1][2][3][4][5][6][7][8][9][10][11][12] As a result, in response to these modulations, molecules can exhibit differences in their ground or excited electronic states, with accompanying modifications in the absorption and/or emission intensity and wavelength. Such changes can be related to the operation of fluorescence chemosensors, molecular switches, and logic gates (via the familiar Boolean logic where the modulators correspond to the inputs and the observed changes correspond to the outputs). [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] As a consequence, the field of molecular logic gates and generally of chemosensors and molecular switches is very active and many research groups around the world work on these subjects. The majority of fluorescence chemosensors and molecular switches are based on the "on-off" or "off-on" response of photoinduced electron transfer (PET), [36][37][38] because PET produces very sharp changes in the signal intensity and it can be modulated in such a way as to generate significant changes in the emission wavelengths. The impact of PET on UV-vis absorption is often negligible and other effects, such as intramolecular charge transfer (ICT) could affect ...

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“…[241][242][243][244] In oximes, the electron density in the NÀ OH bond is shifted towards the electronegative oxygen atom. [241][242][243][244] In oximes, the electron density in the NÀ OH bond is shifted towards the electronegative oxygen atom.…”

Section: Synthesis Of Oximesmentioning

confidence: 99%

Resonance‐Assisted Hydrogen Bonding as a Driving Force in Synthesis and a Synthon in the Design of Materials

Mahmudov

Pombeiro

2016

Chemistry A European J

144

100

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Resonance-assisted hydrogen bonding (RAHB), a concept introduced by Gilli and co-workers in 1989, concerns a kind of intramolecular H-bonding strengthened by a conjugated π-system, usually in 6-, 8-, or 10-membered rings. This Review highlights the involvement of RAHB as a driving force in the synthesis of organic, coordination, and organometallic compounds, as a handy tool in the activation of covalent bonds, and in starting moieties for synthetic transformations. The unique roles of RAHB in molecular recognition and switches, E/Z isomeric resolution, racemization and epimerization of amino acids and chiral amino alcohols, solvatochromism, liquid-crystalline compounds, and in synthons for crystal engineering and polymer materials are also discussed. The Review can provide practical guidance for synthetic chemists that are interested in exploring and further developing RAHB-assisted synthesis and design of materials.

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Intramolecular cyclization of β-nitroso-o-quinone methides. A theoretical endoscopy of a potentially useful innate ‘reclusive’ reaction

Cited by 18 publications

References 86 publications

Theoretical study of the photophysical processes of a styryl‐bodipy derivative eliciting an AND molecular logic gate response

Theoretical study of the photophysical processes of a styryl‐bodipy derivative eliciting an AND molecular logic gate response

The solvent effect on a styryl‐bodipy derivative functioning as an AND molecular logic gate

Resonance‐Assisted Hydrogen Bonding as a Driving Force in Synthesis and a Synthon in the Design of Materials

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