Spectroscopic studies of excited-state intramolecular proton transfer in 1-(acylamino)anthraquinones

Smith, Terrance P.; Zaklika, K. A.; Thakur, Khalid A. M.; Walker, Gilbert C.; Tominaga, Kazuhiro; Barbara, Paul F.

doi:10.1021/j100178a038

Cited by 101 publications

(124 citation statements)

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“…. Most of the publications cited deal with derivatives of salicylic acid, its esters and amides, 18,[20][21][22][23][24][31][32][33]45 o-hydroxybenzaldehyde, acetophenone and related compounds, 19,38,41 o-hydroxybenzoxazoles, 21,42 benzothiazoles, 16,27,37 triazoles, 17,25,30,46 flavonols, 26,29,39,40 anthraquinones, [34][35][36] bipyridyls 28,47,49 and even such a simple model as malonic aldehyde. 48 There have also been several attempts to develop theoretical approaches for the connection between molecular structure and efficiency of ESIPT, for example, Nagaoka and Nagashima 'nodal planes.'…”

Section: Introductionmentioning

confidence: 99%

Excited state intramolecular proton transfer reaction and luminescent properties of theortho-hydroxy derivatives of 2,5-diphenyl-1,3,4-oxadiazole

Дорошенко

Posokhov

Verezubova

et al. 2000

J. Phys. Org. Chem.

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Luminescent properties of several ortho‐hydroxy derivatives of 2,5‐diphenyl‐1,3,4‐oxadiazole were studied in solvents of different polarity and protolytic ability and compared with the analogous derivatives of 1,3‐oxazole, studied by us earlier. Evaluations of rate constants for the excited state intramolecular proton transfer (ESIPT) reaction and radiationless degradation of the energy of electronic excitation in the ESIPT reaction product, phototautomer form, were made on the basis of fluorescence quantum yields and fluorescence kinetic measurements. The proton phototransfer reaction is the most efficient primary photoprocess in the examined series of compounds. With rate constants of 1011–1012 s−1 it exceeds the rates of other primary photophysical processes in these molecules by up to 2–3 orders of magnitude. A connection between the rate of the ESIPT reaction and the electron density redistribution on electronic excitation was revealed for the molecules under study. The electron donor substituents in 5‐phenyl decrease the proton phototransfer rate constant up to complete inhibition of the ESIPT process in the case of the dimethylamino derivative of the oxazole series, whereas the electron acceptor substituents must accelerate this reaction. The determining role of the excited state increase of the proton donor group acidity was assumed on the basis of experimental data and quantum chemical calculations. The temperature investigations showed that the ESIPT reaction in the series of ortho‐hydroxy derivatives of 2,5‐diphenyloxazole and 2,5‐diphenyl‐1,3,4‐oxadiazole has a very low activation barrier. However, the radiationless processes in the phototautomer form are characterized by the presence of a certain barrier in both examined series. A dependence of the radiationless dissipation rate in the phototautomer form on the excited state redistribution of the electron density in it was also found. The more efficient is the charge transfer from the ortho‐phenolate fragment to the protonated heterocycle and the rest of the molecule, the more efficient are the radiationless losses. It was revealed that structural changes, which prevent the mentioned movement of electron density, result in an increase in the fluorescence efficiency of the phototautomer form and, hence, also to an increase in the total fluorescence quantum yield of the ESIPT molecule. Copyright © 2000 John Wiley & Sons, Ltd.

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Section: Introductionmentioning

confidence: 99%

Excited state intramolecular proton transfer reaction and luminescent properties of theortho-hydroxy derivatives of 2,5-diphenyl-1,3,4-oxadiazole

Дорошенко

Posokhov

Verezubova

et al. 2000

J. Phys. Org. Chem.

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“…13 An ESIPT time of 100-300 fs was noted, and tunneling of the localized proton nuclear wave packet was invoked to account for the fast proton transfer. Choi et al reported that ESIPT of 1-hydroxy-anthraquione (1-HAQ) in toluene occurs in 120 fs 18 (260 fs…”

Section: -18mentioning

confidence: 99%

Ultrafast Excited State Intramolecular Proton Transfer Dynamics of 1-Hydroxyanthraquinone in Solution

Ryu¹,

Kim²,

Kim³

et al. 2013

Bulletin of the Korean Chemical Society

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Proton transfer reaction is one of the most fundamental processes in chemistry and life science. Excited state intramolecular proton transfer (ESIPT) has been studied as a model system of the proton transfer, since it can be conveniently initiated by light. We report ESIPT reaction dynamic of 1-hydroxy-anthraquione (1-HAQ) in solution by highly time-resolved fluorescence. ESIPT time of 1-HAQ is determined to be 45 ± 10 fs directly from decay of the reactant fluorescence and rise of the product fluorescence. High time resolution allows observation of the coherent vibrational wave packet motion in the excited state of the reaction product tautomer. The coherently excited vibrational mode involves large displacement of the atoms, which shortens the distance between the proton donor and the acceptor. With the theoretical analysis, we propose that the ESIPT of 1-HAQ proceeds barrierlessly with assistance of the skeletal vibration, which in turn becomes excited coherently by the ESIPT reaction.

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“…The intensity of the orange fluorescence is half of the blue fluorescence intensity. The observation of the dual fluorescence is taken as strong indication to an excited state intramolecular proton transfer (ESIPT) [19][20][21][22][23]. Mostly, the excited-state (S 1 ) tautomer accessed by ESIPT has an energy comparable to or slightly less than that of the normal form, while the ground state (S 0 ) of the tautomer is of considerably higher energy.…”

Section: Scheme 1) Upon Performing Titration Measurements Of Carminimentioning

confidence: 99%

Femtosecond spectroscopic study of carminic acid–DNA interactions

et al. 2006

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Spectroscopic studies of excited-state intramolecular proton transfer in 1-(acylamino)anthraquinones

Cited by 101 publications

References 2 publications

Excited state intramolecular proton transfer reaction and luminescent properties of theortho-hydroxy derivatives of 2,5-diphenyl-1,3,4-oxadiazole

Excited state intramolecular proton transfer reaction and luminescent properties of theortho-hydroxy derivatives of 2,5-diphenyl-1,3,4-oxadiazole

Ultrafast Excited State Intramolecular Proton Transfer Dynamics of 1-Hydroxyanthraquinone in Solution

Femtosecond spectroscopic study of carminic acid–DNA interactions

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