Theoretical study on influence of geometry controlling over the excited-state intramolecular proton transfer of 10-hydroxybenzo[ h ]quinoline and its derivatives

Chansen, Warinthon; Salaeh, Rusrina; Prommin, Chanatkran; Kerdpol, Khanittha; Daengngern, Rathawat; Kungwan, Nawee

doi:10.1016/j.comptc.2017.05.008

Cited by 16 publications

(17 citation statements)

References 46 publications

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“…The observed bathochromic shift supports the strengthening of intramolecular hydrogen bond and probable excited state proton transfer concurrent in the system . The effect of redshift observed is strongly connected to the proton transfer barrier; the stronger the redshift, the lower is the potential barrier and the easier the proton transfer . The stronger the redshift, the weaker the energy of interaction between proton and proton donor.…”

Section: Resultssupporting

confidence: 64%

“…Vibrational frequency analysis of N―H proton donor involved in intramolecular hydrogen bonding substantiates the nature of possible ESIPT present in the system . Han and co‐workers proposed that the observed bathochromic shift or hypsochromic shift at excited state in vibrational spectra strongly correlates with the corresponding strengthening or weakening of intramolecular hydrogen bonding .…”

Section: Resultsmentioning

confidence: 70%

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Exploring the possibilities of double proton transfer in hydrazides: A theoretical approach

Mohan

Satyanarayan

Trivedi

2019

J of Physical Organic Chem

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Hydrazides are known to exhibit keto‐enol tautomerism upon photoexcitation. Theoretical aspects uncovering excited state intramolecular proton transfer (ESIPT) of N‐acylsubstituted hydrazides with bithiophene core have been investigated. Geometrical aspects of the system are expected to undergo double proton translocation at its excited state. However, potential energy surface study for all the molecules reveals an impossible concurrent double proton translocation and to a greater extent dubious step‐wise double proton translocation in the system. Potential energy scans reveal molecules possessing a lower forward barrier at its excited state in comparison with their ground state suggestive of possible excited state single proton transfer. Geometrical attributes and spectral analysis suggest the strengthening of intramolecular hydrogen bond (N―H▪▪▪O) at its excited state, favoring single proton translocation. Theoretical estimation of electronic energy transition for all the conformers yields good correlation with the experimental figures with an energy overestimation <0.17 eV.

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Section: Resultssupporting

confidence: 64%

Section: Resultsmentioning

confidence: 70%

Exploring the possibilities of double proton transfer in hydrazides: A theoretical approach

Mohan

Satyanarayan

Trivedi

2019

J of Physical Organic Chem

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“…From the method of choice, among seven tested functionals, the most suitable method for reproducing the enol absorption spectra of all molecules is the B3LYP because this method provides the most satisfactory agreement with the experimental data. Moreover, previous studies have been proven that the B3LYP and TD-B3LYP functionals with TZVP basis set are suitable to describe electronic and photophysical properties as well as the PT process of ESIPT molecules [29,[57][58][59][60][61][62]. Therefore, the B3LYP was further em ployed to optimize the enol form in the S 1 state and the keto form both in S 0 and the S 1 states of all molecules.…”

Section: Static Calculationsmentioning

confidence: 99%

Heteroatom substitution effect on electronic structures, photophysical properties, and excited-state intramolecular proton transfer processes of 3-hydroxyflavone and its analogues: A TD-DFT study

Sukpattanacharoen

Salaeh

Promarak

et al. 2019

Journal of Molecular Structure

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The effects of the electron-donating capacity altered by heteroatom substituents on the electronic structures, photophysical properties, and excited-state intramolecular proton transfer (ESIPT) processes of 3HX analogues (3HF, 3HQ, 3HTF, and 3HSO where X = O, NH, S, and SO 2 , respectively) have been investigated by both static calculations and dynamic simulations using density functional theory (DFT) and time-dependent DFT (TD-DFT) methods at B3LYP/TZVP level for ground state (S 0 ) and excited-state (S 1 ), respectively. The static results indicate that the intramolecular hydrogen bonds of all molecules are strengthened in the S 1 , confirmed by the red-shift of IR vibrational spectra and the topology analysis. Heteroatom substitutions cause the red-shift on enol absorption and keto emission spectra of 3HX with relatively larger Stoke shift corresponding to their HOMO−LUMO gaps compared with that of 3HF. Frontier molecular orbitals (MOs) show that upon the photoexcitation, the charge redistribution between the proton donor and proton acceptor groups have induced the ESIPT process. Moreover, the potential energy curves (PECs) of proton transfer (PT) processes of all molecules reveal that the PT processes of all molecules are most likely to proceed in the S 1 state because of low barriers and exothermic reaction. The chance of ESIPT for all molecules is in this order: 3HSO > 3HTF > 3HF > 3HQ. The results of dynamic simulations confirm that the ESIPT processes of all molecules easily occur with the ultrafast time scale (48, 55, 60, 70 fs for 3HSO, 3HTF, 3HF, and 3HQ, respectively). Furthermore, the PT time is anti-correlated with the electronegativity of heteroatoms in 3HX, supported by Mulliken analysis. The ESIPT process of 3HSO is the fastest among 3HX in accordance with its highest intramolecular hydrogen bond strength, lowest PT barrier, and highest exothermic reaction. Nevertheless, after the ESIPT is complete, the twisted structure of 3HSO has initiated the conical intersection, leading to no keto emission observed in the experiment.

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“…Here, we report the iEIPT capability of 10-hydroxybenzo[h]quinoline (HBQ) and 8-hydroxyquinoline (HQ), both of which have been shown to display ESIPT properties 24 – 32 , especially the former, HBQ, was extensively studied both experimentally and theoretically 24 – 31 . Here the iEIPT of these two molecules are studied by mass spectrometry and photoelectron spectroscopy, and the experimental results are then validated by density functional theory (DFT) calculations.…”

Section: Introductionmentioning

confidence: 99%

Intramolecular electron-induced proton transfer and its correlation with excited-state intramolecular proton transfer

et al. 2019

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Electron-induced proton transfer depicts the proton motion coupled with the attachment of a low-energy electron to a molecule, which helps to understand copious fundamental chemical processes. Intramolecular electron-induced proton transfer is a similar process that occurs within a single molecule. To date, there is only one known intramolecular example, to the best of our knowledge. By studying the 10-hydroxybenzo[h]quinoline and 8-hydroxyquinoline molecules using anion photoelectron spectroscopy and density functional theory, and by theoretical screening of six other molecules, here we show the intramolecular electron-induced proton transfer capability of a long list of molecules that meanwhile have the excited-state intramolecular proton transfer property. Careful examination of the intrinsic electronic signatures of these molecules reveals that these two distinct processes should occur to the same category of molecules. Intramolecular electron-induced proton transfer could have potential applications such as molecular devices that are responsive to electrons or current.

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Theoretical study on influence of geometry controlling over the excited-state intramolecular proton transfer of 10-hydroxybenzo[ h ]quinoline and its derivatives

Cited by 16 publications

References 46 publications

Exploring the possibilities of double proton transfer in hydrazides: A theoretical approach

Exploring the possibilities of double proton transfer in hydrazides: A theoretical approach

Heteroatom substitution effect on electronic structures, photophysical properties, and excited-state intramolecular proton transfer processes of 3-hydroxyflavone and its analogues: A TD-DFT study

Intramolecular electron-induced proton transfer and its correlation with excited-state intramolecular proton transfer

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