Hydrogen bond capability tunable different “relay-race” mechanisms of the excited-state proton transfer process for 4′-methoxy-3-hydroxyflavone

Li, Hui; Xin, Chao; Cai, Jixing; Yuan, Boshi; Wei, Zheng; Jin, Guangyong

doi:10.1016/j.orgel.2020.105678

Cited by 9 publications

(4 citation statements)

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“…The potential transfer channels of 2a-MeOH were considered to have three types which were depicted alongside the energy curves. [52] The stepwise mechanism is discussed firstly. The proton transferred from solute 2a to solvent MeOH (type 1) or from solvent MeOH to solute 2a (type 2), each proton transfer process occurs sequentially.…”

Section: Potential Energy Curvesmentioning

confidence: 99%

Theoretical investigation of fluorescence changes caused by methanol bridge based on ESIPT reaction*

Zhang¹,

Zhu²,

Wang³

et al. 2021

Chinese Phys. B

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The different fluorescence behavior caused by the excited state proton transfer in 3-hydroxy-4-pyridylisoquinoline (2a) compound has been theoretically investigated. Our calculation results illustrate that the 2a monomer in tetrahydrofuran solvent would not occur proton transfer spontaneously, while the 2a complex in methanol (MeOH) solvent can undergo an asynchronous excited state intramolecular proton transfer (ESIPT) process. The result was confirmed by analyzing the related structural parameters, infrared vibration spectrum and reduced density gradient isosurfaces. Moreover, the potential curves revealed that with the bridging of single MeOH molecular the energy barrier of ESIPT was modulated effectively. It was distinctly reduced to 4.80 kcal/mol in 2a-MeOH complex from 25.01 kcal/mol in 2a monomer. Accordingly, the ESIPT process induced a fluorochromic phenomenon with the assistant of proton-bridge. The elucidation of the mechanism of solvent discoloration will contribute to the design and synthesis of fluorogenic dyes as environment-sensitive probes.

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Section: Potential Energy Curvesmentioning

confidence: 99%

Theoretical investigation of fluorescence changes caused by methanol bridge based on ESIPT reaction*

Zhang¹,

Zhu²,

Wang³

et al. 2021

Chinese Phys. B

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“…A low intensity band associated with its anionic form appears at longer wavelengths. From a theoretical point of view, the UV–vis spectrum and the ESIPT of 3-HF − and 3-HF-based chromophores − have been studied both in gas phase and in solution. Most of these studies have used TDDFT, although MNDO/AM1, , CIS, and CASPT2/CASSCF methods have also been applied.…”

Section: Introductionmentioning

confidence: 99%

A Theoretical Study of Solvent Effects on the Structure and UV–vis Spectroscopy of 3-Hydroxyflavone (3-HF) and Some Simplified Molecular Models

2023

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Solvent effects on the UV–vis spectra of 3-hydroxyflavone and other structurally related molecules (3-hydroxychromen-4-one, 3-hydroxy-4-pyrone, and 4-pyrone) have been studied by combining time-dependent density functional theory (TDDFT) and the polarizable continuum method (PCM). Among the first five excited states of the four considered molecules, electronic states of n → π* and π → π* nature appear. In general, the stability of the n → π* states decreases as the π space becomes larger in such a way that only for 4-pyrone and 3-hydroxy-4-pyrone are they the first excited states. In addition, they become less stabilized in ethanol solution than the ground state, and this causes blueshift transitions in solution. The opposite trend is found for the π → π* excited states. They are less energetic with the π-system size and when passing from gas phase to solution. The solvent shift also depends strongly on the size of the π systems and on the formation of an intramolecular hydrogen bond; thus, it decreases when going from 4-pyrone to 3-hydroxyflavone. The performance of the three versions (cLR, cLR2, and IBSF) of the specific-state PCM method in predicting transition energies are compared.

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“…In spite of the simplicity implied by this superficial explanation, PT reactions have been the subject F I G U R E 1 Reaction mechanism for isomerization of hydroxyacetone to 2-hydroxypropanal of numerous experimental [15][16][17][18][19] and theoretical [20][21][22][23] studies for decades. This fascination with PT reactions stems from the many unique scenarios they are involved in, for instance they occur in both intermolecular [24] and intramolecular [25] reactions, ground state thermal-induced processes, [26][27][28] excited state photoinduced processes, [29][30][31][32] and even processes coupled with electron transfer. [33] Each scenario presenting a unique set of physical challenges.…”

Section: Introductionmentioning

confidence: 99%

Intramolecular Proton Transfer in the Isomerization of Hydroxyacetone: A Detailed Characterization Based on Reaction Force Analysis and the Bond Fragility Spectrum

Derricotte

Joseph²

2020

Preprint

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The mechanism of isomerization of hydroxyacetone to 2-hydroxypropanal is studied within the framework of reaction force analysis at the M06-2X/6-311++G(d,p) level of theory. Three unique pathways are considered: (i) a step-wise mechanism that proceeds through formation of the Z-isomer of their shared enediol intermediate, (ii) a step-wise mechanism that forms the E-isomer of the enediol, and (iii) a concerted pathway that bypasses the enediol intermediate. Energy calculations show that the concerted pathway has the lowest activation energy barrier at 45.7 kcal mol<sup>-1</sup>. The reaction force, chemical potential, and reaction electronic flux are calculated for each reaction to characterize electronic changes throughout the mechanism. The reaction force constant is calculated in order to investigate the synchronous/asynchronous nature of the concerted intramolecular proton transfers involved. Additional characterization of synchronicity is provided by calculating the bond fragility spectrum for each mechanism.

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Hydrogen bond capability tunable different “relay-race” mechanisms of the excited-state proton transfer process for 4′-methoxy-3-hydroxyflavone

Cited by 9 publications

References 50 publications

Theoretical investigation of fluorescence changes caused by methanol bridge based on ESIPT reaction*

Theoretical investigation of fluorescence changes caused by methanol bridge based on ESIPT reaction*

A Theoretical Study of Solvent Effects on the Structure and UV–vis Spectroscopy of 3-Hydroxyflavone (3-HF) and Some Simplified Molecular Models

Intramolecular Proton Transfer in the Isomerization of Hydroxyacetone: A Detailed Characterization Based on Reaction Force Analysis and the Bond Fragility Spectrum

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