Effective targeting of proton transfer at ground and excited states of ortho-(2′-imidazolyl)naphthol constitutional isomers

Oliveira, Thaís C. F.; Carmo, Luiz F. V.; Murta, Bárbara; Duarte, Luís Gustavo Teixeira Alves; Nome, René A.; Rocha, Willian R.; Brandão, Tiago A. S.

doi:10.1039/c4cp04337e

Cited by 14 publications

(26 citation statements)

References 69 publications

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“…Furthermore, the hydrogen bond strengthening or weakening could also be revealed based on monitoring the spectral shifts of vibrational modes involved in the formation of hydrogen bonds . The vibrational spectra of bip chromophore in the conjunct vibrational regions of the O‐H stretching mode have been shown in Figure .…”

Section: Resultsmentioning

confidence: 99%

“…The geometric optimizations of bip , bip‐open and bip‐pt were performed using DFT in the S 0 state and using TDDFT in the S 1 state. Especially, the TDDFT method has become a very useful tool to theoretically investigate the hydrogen bonding interaction that occurs in the excited states . In addition, Becke's three‐parameter hybrid exchange functional with Lee–Yang–Parr gradient‐corrected correlation (B3LYP functional) was selected in both the DFT and TDDFT methods .…”

Section: Theoretical Methodsmentioning

confidence: 99%

“…Till now, many different sensing mechanisms, such as intramolecular charge transfer (ICT), photo‐induced electron transfer (PET), fluorescence resonance energy transfer (FRET), and excited state proton transfer (ESPT) and so forth, are relevant with intra‐ or inter‐ molecular hydrogen bond. Particularly, the excited state inter‐ and intra‐ molecular proton transfer (ESIPT) reactions have been drawing great attention due to their unique photo‐physical and photo‐chemical properties.…”

Section: Introductionmentioning

confidence: 99%

“…Even though this sensor has weak fluorescence, it was reported that the anion‐binding adduct of bip is expected to be highly fluorescent based on ESIPT channel experimentally, however, the mechanism of bip in excited state is very limitted. In effect, experimental spectroscopic techniques, such as steady‐state absorption spectroscopy, fluorescence spectroscopy and time resolved fluorescence spectroscopy, just provide the indirect information about photo‐physical and photo‐chemical properties . Up to now, the theoretical investigations about the bip are very scarce in addition to the experiments.…”

Section: Introductionmentioning

confidence: 99%

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The revelation of ESIPT behavior and fluoride response mechanism for (E)‐2‐(((1H‐benzo[d]imidazol‐2‐yl)‐imino)methyl)‐5‐(dimethylamino)‐phenol

Zheng

Zhang

et al. 2019

J of Physical Organic Chem

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Given the tremendous potential of fluorescence sensors in recent years, in this work, as a kind of novel and few studied sensor containing both NH and OH binding sites, (E)-2- (((1H-benzo[d]imidazol-2-yl)-imino)methyl)-5-(dimethylamino)-phenol (bip) has been investigated on the excited state intramolecular proton transfer (ESIPT) based on time-dependent density functional theory (TDDFT) method. Our simulated absorption and fluorescence spectra based on the TDDFT method are in agreement with the experimental results.Two kinds of bip structures could found in the S 1 state, which could be attributed to the ESIPT reaction. Hydrogen bond strengthening has been testified in the S 1 state based on comparing staple bond lengths and bond angles involved in hydrogen bond between S 0 and S 1 states. The calculated infrared (IR) vibrational spectra at the O-H stretching vibrational region and theoretical hydrogen bonding energy also declare the phenomenon of hydrogen bond strengthening. The frontier molecular orbitals (MOs) analysis and Natural bond orbital (NBO) manifest the intramolecular charge transfer (ICT) characteristic for bip chromophore, which reveals the tendency of proton transfer.The potential energy curvess of the S 0 and S 1 states are constructed to explain the mechanism of the proton transfer in excited state in detail. Further, given fluorescence sensing mechanism, we present the addition of fluoride anion can spontaneously capture the hydrogen proton of hydroxyl forming intermolecular hydrogen bond O-H···F, which results in the formation of anion product with response fluoride anion.

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Section: Resultsmentioning

confidence: 99%

Section: Theoretical Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The revelation of ESIPT behavior and fluoride response mechanism for (E)‐2‐(((1H‐benzo[d]imidazol‐2‐yl)‐imino)methyl)‐5‐(dimethylamino)‐phenol

Zheng

Zhang

et al. 2019

J of Physical Organic Chem

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“…Excited‐state intramolecular proton transfer (ESIPT), as one of the most important excited‐state hydrogen bond reactions in chemistry and biology, is prevalent throughout the nature . Therefore, the investigation of the photo‐induced proton transfer (PT) reaction involved in the intramolecular hydrogen bond has attracted vast attention based on both theoretical and experimental techniques . In fact, the most important indications of the occurrence of ESIPT could be provided by fluorescence spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

Theoretical investigation on the excited-state intramolecular proton transfer mechanism of 2-(2′-benzofuryl)-3-hydroxychromone

2015

J. Phys. Org. Chem.

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Spectroscopic studies on excited-state proton transfer of a new chromophore 2-(2′-benzofuryl)-3-hydroxychromone (BFHC) have been reported recently. In the present work, based on the time-dependent density functional theory (TD-DFT), the excited-state intramolecular proton transfer (ESIPT) of BFHC is investigated theoretically. The calculated primary bond lengths and angles involved in hydrogen bond demonstrate that the intramolecular hydrogen bond is strengthened. In addition, the phenomenon of hydrogen bond reinforce has also been testified based on infrared (IR) vibrational spectra as well as the calculated hydrogen bonding energies. Further, hydrogen bonding strengthening manifests the tendency of excited state proton transfer. Our calculated results reproduced absorbance and fluorescence emission spectra of experiment, which verifies that the TD-DFT theory we used is reasonable and effective. The calculated Frontier Molecular Orbitals (MOs) further demonstrate that the excited state proton transfer is likely to occur. According to the calculated results of potential energy curves along O-H coordinate, the potential energy barrier of about 14.5 kcal/mol is discovered in the S 0 state. However, a lower potential energy barrier of 5.4 kcal/mol is found in the S 1 state, which demonstrates that the proton transfer process is more likely to happen in the S 1 state than the S 0 state. In other words, the proton transfer reaction can be facilitated based on the photo-excitation effectively. Moreover, the phenomenon of fluorescence quenching could be explained based on the ESIPT mechanism.

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The invalidity of intermolecular proton transfer triggered twisted intramolecular charge transfer in excited state for 2‐(4′‐diethylamino‐2′‐hydroxyphenyl)‐1H‐imidazo‐[4,5‐b]pyridine

Qinye

Peng

Liu

2022

J Chinese Chemical Soc

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The excited-state dynamics of the excited-state proton transfer and intramolecular twisted charge transfer (TICT) reactions of a molecular photoswitch 2-( 40diethylamino-2 0 -hydroxyphenyl)-1H-imidazo-[4,5-b]pyridine (DHP) in aprotic and alcoholic solvents have been theoretically investigated by using time-dependent density functional theory. The excited-state intramolecular proton transfer (ESIPT) reaction of DHP proceeding upon excitation in all the solvents has been confirmed, and the dual emission has been assigned to the enol and keto forms of DHP. However, for methanol and ethanol solvents within strong hydrogen-bonded capacity, the intermolecular hydrogen bonds between DHP and methanol/ethanol would promote an excitedstate double proton transfer (ESDPT) along the hydrogen-bonded bridge. Importantly, the previous proposed ESDPT-triggered TICT mechanism of DHP in methanol and ethanol was not supported by our calculations. The twist motion would increase the total energy of the system for both the products of ESIPT and ESDPT. According to the calculations of the transition states, the ESDPT reaction occurs much easier in keto form generated by ESIPT. Therefore, a sequential ESIPT and ESDPT mechanism of DHP in methanol and ethanol has been reasonably proposed. K E Y W O R D S excited-state proton transfer, hydrogen bond, intramolecular twisted charge transfer, timedependent density functional theory

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Effective targeting of proton transfer at ground and excited states of ortho-(2′-imidazolyl)naphthol constitutional isomers

Cited by 14 publications

References 69 publications

The revelation of ESIPT behavior and fluoride response mechanism for (E)‐2‐(((1H‐benzo[d]imidazol‐2‐yl)‐imino)methyl)‐5‐(dimethylamino)‐phenol

The revelation of ESIPT behavior and fluoride response mechanism for (E)‐2‐(((1H‐benzo[d]imidazol‐2‐yl)‐imino)methyl)‐5‐(dimethylamino)‐phenol

Theoretical investigation on the excited-state intramolecular proton transfer mechanism of 2-(2′-benzofuryl)-3-hydroxychromone

The invalidity of intermolecular proton transfer triggered twisted intramolecular charge transfer in excited state for 2‐(4′‐diethylamino‐2′‐hydroxyphenyl)‐1H‐imidazo‐[4,5‐b]pyridine

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