TDDFT study of twisted intramolecular charge transfer and intermolecular double proton transfer in the excited state of 4′-dimethylaminoflavonol in ethanol solvent

Wang, Ye; Shi, Ying; Lin, Cong; Li, Hui

doi:10.1016/j.saa.2014.09.024

Cited by 60 publications

(22 citation statements)

References 52 publications

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“…That is to say, the hydrogen bond N-H•••N should be strengthened in the S 1 state for both ABO and ABT systems based on the photo-excitation [65][66][67][68][69][70][71][72][73][74][75][76][77]. Moreover, spectral shift with special vibrational modes can be also used to detect the electronic excited-state hydrogen bond dynamics [65][66][67][68][69][70][71][72][73][74][75][76][77]. The S 0 -state and S 1 -state infrared (IR) vibrational spectra of ABO and ABT at the spectral region of N-H stretching band have been shown in Figure 2.…”

Section: Resultsmentioning

confidence: 99%

“…Also for ABT-enol structure, a red shift 265 cm -1 can be lead to from S 0 -state 3502 cm -1 to S 1 -state 3237 cm -1 . This phenomenon indicates that the intramolecular hydrogen bond N-H•••N should be reinforced in the S 1 state [65][66][67][68][69][70][71][72][73][74][75][76][77]. Furthermore, according to the relationship between bond energy EHB and potential energy density V(r) at corresponding BCP could be approximately described as EHB=V(r)/2 [63], we also estimate the hydrogen bonding energies for ABO and ABT systems in both S 0 and S 1 states.…”

Section: Resultsmentioning

confidence: 99%

“…All these agreements with previous experimental reports demonstrate that the theoretical excited state of ABO and ABT systems based on the TDDFT/B3LYP/TZVP theoretical level can delineate the excited-state characteristics well. It is well known that the changes about charge distribution bringing from the photo-excitation process are closely related to excited state dynamical behaviors [65][66][67][68][69][70][71][72][73][74][75][76][77], therefore, it is necessary to qualitatively explore the charge redistribution in electronic excited states. In this work, the charge distributions and charge transfers in the excited states are examined using the frontier molecular orbitals (MOs) methods.…”

Section: Resultsmentioning

confidence: 99%

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Theoretical insights into the excited state hydrogen bond and ESIPT reaction for 2-amino-3-(2’-benzoxazolyl)quinoline and 2-amino-3-(2’-benzothiazolyl)-quinoline

Zhang¹

2018

JAMS

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Two N-H type excited state intramolecular proton transfer (ESIPT) systems (i.e., 2-amino-3-(2'benzoxazolyl)quinoline (ABO) and 2-amino-3-(2'-benzothiazolyl)-quinoline (ABT)) have been investigated. Adopting DFT and TDDFT methods coupling with B3LYP functional and TZVP basis set, our simulations about ABO and ABT molecules have successfully reappeared experimental results, based on which the rationality of our calculations is confirmed. Using Atoms in Molecules (AIM) analytical method, we firstly explore the interactions about chemical bond and verify the formation of hydrogen bond N-H•••N for ABO and ABT in the S 0 state. Investigating the primary geometrical parameters involved in N-H•••N, we find it should be strengthened in the S 1 state. Upon photoexcitation, charge transfer phenomenon is found via frontier molecular orbitals (MOs), and charge redistribution provides the tendency of ESIPT reaction for ABO and ABT. According to our constructed potential energy curves of both S 0 and S 1 states for ABO and ABT using two kinds of methods (i.e., the elongation of N-H single bond and the weakening of H•••N hydrogen bond), we clarify the ESIPT mechanisms and explain the recovery of four-level reaction cycle. Our searching transition state (TS) structures and simulated intrinsic reaction coordinate (IRC) path further confirm the ESIPT reaction.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Theoretical insights into the excited state hydrogen bond and ESIPT reaction for 2-amino-3-(2’-benzoxazolyl)quinoline and 2-amino-3-(2’-benzothiazolyl)-quinoline

Zhang¹

2018

JAMS

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“…The general ESIPT process starts from the ground-state enol form and ends by returning to the same state after the so-called four-level reaction cycle. [27][28][29][30][31][32][33][34][35][36][37][38] Most recent cutting-edge application seems to be focused on lighting materials. The difference between the two Stokes shifts could be as large as 6,000-12,000 cm −1 .…”

Section: Introductionmentioning

confidence: 99%

A detailed theoretical study on the excited‐state hydrogen‐bonding dynamics and the proton transfer mechanism for a novel white‐light fluorophore

Gao

Yang

Jia

et al. 2018

J Chinese Chemical Soc

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In this work, density functional theory (DFT) and time‐dependent DFT (TDDFT) methods were used to investigate the excited‐state dynamics of the excited‐state hydrogen‐bonding variations and proton transfer mechanism for a novel white‐light fluorophore 2‐(4‐[dimethylamino]phenyl)‐7‐hyroxy‐6‐(3‐phenylpropanoyl)‐4H‐chromen‐4‐one (1). The methods we adopted could successfully reproduce the experimental electronic spectra, which shows the appropriateness of the theoretical level in this work. Using molecular electrostatic potential (MEP) as well as the reduced density gradient (RDG) versus the product of the sign of the second largest eigenvalue of the electron density Hessian matrix and electron density (sign[λ2]ρ), we demonstrate that an intramolecular hydrogen bond O1–H2···O3 should be formed spontaneously in the S0 state. By analyzing the chemical structures, infrared vibrational spectra, and hydrogen‐bonding energies, we confirm that O1–H2·O3 should be strengthened in the S1 state, which reveals the possibility of an excited‐state intramolecular proton transfer (ESIPT) process. On investigating the excitation process, we find the S0 → S1 transition corresponding to the charge transfer, which provides the driving force for ESIPT. By constructing the potential energy curves, we show that the ESIPT reaction results in a dynamic equilibrium in the S1 state between the forward and backward processes, which facilitates the emission of white light.

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“…Meanwhile, the most significant Stokes shift could be observed for keto* form, and this shift can be as large as 8000 to 12 000 cm ‐1 . Just due to this kind of fluorescence properties for ESIPT reaction, this process can facilitate charge redistribution, and based on which lots of applications about ESIPT molecules have been reported, such as laser dyes, LEDs, fluorescence sensors, molecular switches, and so forth …”

Section: Introductionmentioning

confidence: 99%

The excited state hydrogen bond and proton transfer mechanism of a novel dye CS‐Azine

Jia

Yang

Song

et al. 2018

J of Physical Organic Chem

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In this work, based on density functional theory (DFT) and time‐dependent DFT (TDDFT) methods, we theoretically explore the excited state behavior for a novel dye molecule 3,3′‐(5,5′‐((1E,1E′)‐hydrazine‐1,2‐diylidenebis (methanylylidene))bis(2‐morpholinothiazole‐5,4‐diyl))bis(4‐hydroxy‐2H‐chromen‐2‐one) (CS‐Azine). Coupling with atoms in molecules, we investigate the intramolecular dual hydrogen bonds of CS‐Azine system and verify the formation of them. Via study the primary bond distances, bond angle, and infrared vibrational spectra involved in hydrogen bonding moieties, we find O1‐H2···N3 and O4‐H5···N6 of CS‐Azine should be strengthened in the S1 state. When exploring the photo‐excitation process, we confirm that the charge redistribution around hydrogen bonding moieties reveals the tendency of ESIPT reaction. To further investigate whether single or double proton transfer occurs in the S1 state, we consider two kinds of reaction paths (ie, the stepwise and synergetic ESIPT reactions). And the constructed potential energy curves demonstrate that only the single proton transfer reaction should be the most supported in the S1 state from CS‐Azine to CS‐Azine‐SPT form due to the low potential energy barrier. This work not only clarifies the excited state behavior and mechanism about CS‐Azine system but also paves the way for further applying CS‐Azine dye in future.

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TDDFT study of twisted intramolecular charge transfer and intermolecular double proton transfer in the excited state of 4′-dimethylaminoflavonol in ethanol solvent

Cited by 60 publications

References 52 publications

Theoretical insights into the excited state hydrogen bond and ESIPT reaction for 2-amino-3-(2’-benzoxazolyl)quinoline and 2-amino-3-(2’-benzothiazolyl)-quinoline

Theoretical insights into the excited state hydrogen bond and ESIPT reaction for 2-amino-3-(2’-benzoxazolyl)quinoline and 2-amino-3-(2’-benzothiazolyl)-quinoline

A detailed theoretical study on the excited‐state hydrogen‐bonding dynamics and the proton transfer mechanism for a novel white‐light fluorophore

The excited state hydrogen bond and proton transfer mechanism of a novel dye CS‐Azine

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