On the intramolecular proton transfer of 3-hydroxyflavone in the first singlet excited state: A theoretical study

Casadesús, Ricard; Vendrell, Oriol; Moreno, Miquel; Lluch, José M.; Morokuma, Keiji

doi:10.1016/j.chemphys.2005.12.028

Cited by 38 publications

(36 citation statements)

References 44 publications

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“…Clearly, all of them have π-type symmetry, so the S 0 →S 1 transition, which is from HOMO→LUMO transition, can be ascribed to π → π* excitation. 30,31 As shown in Figure 2, electron moved along conjugated chain (Ph-C＝C-Ph-N＝C-Ph) towards the same side as substituent groups of C1 and C2 from HOMO to LUMO both in S 0 and S 1 state, and the electron density distribution of phenol ring was diminished owing to withdrawing electron effects of nitro and cyano groups. While as contrast, because the electron-donating effects of methoxyl and N,N-diethylamino groups, electron moved to opposite side to substituent groups of molecules along conjugated chain (Ph-C＝C-Ph-N＝C-Ph), and the electron density distribution of phenol ring was increased in C3 and C4.…”

Section: Frontier Molecular Orbitsmentioning

confidence: 99%

Photoinduced Excited State Intramolecular Proton Transfer of New Schiff Base Derivatives with Extended Conjugated Chromophores: A Comprehensive Theoretical Survey

Wang¹,

Gao²,

Li³

et al. 2010

Chin. J. Chem.

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This paper presented comprehensive theoretical investigation of excited state intramolecular proton transfer (ESIPT) of four new large Schiff base derivatives with extended conjugated chromophores. The properties of the ground state and the excited state of phototautomers of C1 to included geometrical parameter, energy, rate constant, frontier orbit, Mulliken charge, dipole moment change, were studied by DFT (density functional theory), CIS (configuration interaction singles-excitation), TDDFT (time-dependent DFT) methods to analyze the effects of chromophore part on the occurrence of ESIPT and the role of substituent groups. The structural parameter calculation showed that the shorter R H-N and larger R O-H from enol to enol* form, and less twisted configuration in the excited state implied that these molecules could undergo ESIPT as excitation. Stable transition states and a low energy barrier were observed for C1 to C4. This suggested that chromophore part increased some difficulty to undergo ESIPT for these molecules, while the possibility of occurrence of ESIPT was quite high. The negative ∆E * (-9.808 and -9.163 kJ/mol) of C1 and C2 and positive ∆E * (0.599 and 1.029 kJ/mol) of C3 and C4 indicated that withdrawing substituent groups were favorable for the occurrence of ESIPT. The reaction rate constants of proton transfer of these compounds were calculated in the S 0 and S 1 states respectively, and the high rate constants of these compounds were observed at S 1 state. C1 even reached at 1.45×10 15 s -1 in the excited state, which is much closed to 2.05×10 15 s -1 of the parent moiety (salicylidene methylamine). Electron-donating and electron-withdrawing substituent groups had different effects on the electron density distribution of frontier orbits and Mulliken charges of the atoms, resulting in different dipole moment changes in enol*→keto* process. These differences in turn suggested that C1 and C2 had more ability to undergo ESIPT than C3 and C4. The ultraviolet/visible absorption spectra, normal fluorescence emission spectra and ESIPT fluorescence emission spectra of these compounds were predicted in theory.

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Section: Frontier Molecular Orbitsmentioning

confidence: 99%

Photoinduced Excited State Intramolecular Proton Transfer of New Schiff Base Derivatives with Extended Conjugated Chromophores: A Comprehensive Theoretical Survey

Wang¹,

Gao²,

Li³

et al. 2010

Chin. J. Chem.

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“…[27][28][29][30] Furthermore a variety of theoretical investigations have been performed. [31][32][33][34][35][36][37][38][39] The direct structural proof for the ESPT of isolated 3-HF in the gas phase was given by our group by applying structure sensitive combined IR/UV methods (IR/R2PI for the S 0 state and UV/IR/UV for the S 1 state) under isolated molecular beam conditions. 30 In comparison to the calculated vibrational frequencies of different (TD)-DFT optimised structures the presence of the tautomeric form in the electronically excited state could be demonstrated not only for 3-HF but also for 2-(2-naphthyl)-3-hydroxychromone (2-NHC), a derivative, differing in the naphthyl substituent on the chromone moiety.…”

Section: Introductionmentioning

confidence: 99%

A combined IR/IR and IR/UV spectroscopy study on the proton transfer coordinate of isolated 3-hydroxychromone in the electronic ground and excited state

Stamm

Weiler

Brächer

et al. 2014

Phys. Chem. Chem. Phys.

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In this paper the excited state proton transfer (ESPT) of isolated 3-hydroxychromone (3-HC), the prototype of the flavonols, is investigated for the first time by combined IR/UV spectroscopy in molecular beam experiments. The IR/UV investigations are performed both for the electronically excited and electronic ground state indicating a spectral overlap of transitions of the 3-HC monomer and clusters with water in the electronic ground state, whereas in the excited state only the IR frequencies of the proton-transferred monomer structure are observed. Due to the loss of isomer and species selectivity with respect to the UV excitations IR/IR techniques are applied in order to figure out the assignment of the vibrational transitions in the S0 state. In this context the quadruple resonance IR/UV/IR/UV technique (originally developed to distinguish different isomers in the electronically excited state) could be applied to identify the OH stretching vibration of the monomer in the electronic ground state. In agreement with calculations the OH stretching frequency differs significantly from the corresponding values of substituted hydroxychromones.

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“…The dramatic enhancement of experimental resolution has been paralleled by a steady increase in computing power, accelerating theoretical study [14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31]. One of the most popular molecular 'families' for studying ESIPT has been salicylic acid and its derivatives [5,[10][11][12][14][15][16][17][18][19][20]24,26,27,[32][33][34][35][36], and we have previously presented computational analyses of the phenomenon in malonaldehyde (MA) [14,37] and methyl salicylate (MS) [15].…”

Section: Introductionmentioning

confidence: 99%

Ab initio multiple spawning dynamics of excited state intramolecular proton transfer: the role of spectroscopically dark states

Coe

Martı́nez

2008

Molecular Physics

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Excited state intramolecular proton transfer (ESIPT) and electronic relaxation in o-hydroxybenzaldehyde (OHBA) are simulated using ab initio multiple spawning (AIMS) dynamics, and the results are compared with those obtained for the closely related molecules malonaldehyde and methyl salicylate. The role of electronic state ordering (more specifically, the placement of spectroscopically dark states) is examined in the context of tautomerisation yield. When a state of n* character lies between the optically accessible state and S 0 , the extent of ESIPT is hindered.

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On the intramolecular proton transfer of 3-hydroxyflavone in the first singlet excited state: A theoretical study

Cited by 38 publications

References 44 publications

Photoinduced Excited State Intramolecular Proton Transfer of New Schiff Base Derivatives with Extended Conjugated Chromophores: A Comprehensive Theoretical Survey

Photoinduced Excited State Intramolecular Proton Transfer of New Schiff Base Derivatives with Extended Conjugated Chromophores: A Comprehensive Theoretical Survey

A combined IR/IR and IR/UV spectroscopy study on the proton transfer coordinate of isolated 3-hydroxychromone in the electronic ground and excited state

Ab initio multiple spawning dynamics of excited state intramolecular proton transfer: the role of spectroscopically dark states

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