Excited state intramolecular proton transfer of 1,2-dihydroxyanthraquinone by femtosecond transient absorption spectroscopy

1,2-Dihydroxyanthraquinone (alizarin) shows dual emission bands with a large Stokes shift from a “locally-excited (LE)” and “proton-transferred (PT)” tautomers in the excited state. Excited state intramolecular proton transfer (ESIPT) reaction of alizarin is tunable by changing concentration, solvent polarity, excitation wavelength, and etc. ESIPT reaction of alizarin in the excited state was investigated by steady-state absorption/emission spectroscopy and femtosecond transient absorption spectroscopy. In ethanol solution, the lifetime of PT tautomer of alizarin was measured as 87 ps, in addition to 0.35 and 8.3 ps vibrational cooling dynamics for the LE and PT tautomers of alizarin, respectively. In binary mixtures of ethanol and water, the excited state dynamics became more complicated; the LE and PT tautomers appeared to decay with 8.9 and 30.8 ps lifetimes, which is much shorter compared to the lifetime of the PT tautomer in ethanol. A long-lived nonradiative state in the excited states of alizarin was found as well, which was proposed as a “trapped” state with tightly hydrogen-bonded water molecules. The ESIPT reaction of alizarin was blocked in a 1:1 mixture of ethanol-water due to strong hydrogen bonding between water molecules and alizarin, which was further confirmed by the efficient coupling of alizarin to TiO₂ nanoparticles in the 1:1 binary mixture of ethanol-water.     

The substituent effect on the excited state intramolecular proton transfer of 3-hydroxychromone

The excited state intramolecular proton transfer of four derivatives(FM, BFM, BFBC, CCM) of 3-hydroxychromone is investigated.The geometries of different substituents are optimized to study the substituent effects on proton transfer.The mechanism of hydrogen bond enhancement is qualitatively elucidated by comparing the infrared spectra, the reduced density gradient, and the frontier molecular orbitals.The calculated electronic spectra are consistent with the experimental results.To quantify the proton transfer, the potential energy curves(PECs) of the four derivatives in S_0 and S_1 states are scanned.It is concluded that the ability of proton transfer follows the order: FM BFM BFBC CCM.     

Lead chloride-based layered perovskite incorporated with an excited state intramolecular proton transfer dye

We successfully fabricated thin films of organic–inorganic layered perovskite-type compound (AEHBA)₂PbCl₄, where AEHBA stands for N-(2-aminoethyl)-2-hydroxybenzamide, a blue fluorescent dye that shows excited state intramolecular proton transfer (ESIPT) reaction. The formation of its highly ordered structure was readily achieved by the spin-coating of N,N-dimethylformamide solution dissolving PbCl₂ and the AEHBA hydrogen chloride salt. X-ray diffraction analysis of the films revealed that organic AEHBA and inorganic PbCl₄ perovskite layers were alternately stacked parallel to the substrate. In the absorption spectrum, exciton formation within the perovskite layers was confirmed by the appearance of a characteristic sharp band, while the photoluminescence spectrum showed a large Stokes-shifted band of AEHBA, indicating that it underwent an ESIPT.     

Mathematical modeling of photoisomerization with intramolecular proton transfer

A system of equations describing time changes in the matrix elements of the density operator of a seven-level model of a molecule interacting with a light pulse taking into account spontaneous (including collective) decays of molecule excited states is suggested. Model parameters were selected to allow us to perform modeling of the photoisomerization of a molecule with two isomeric states with different stable proton positions on an intramolecular H-bond by numerically solving the suggested system of equations for density operator matrix elements. An analysis of the characteristic time dependences of the population of states of the model under consideration showed that proton phototransfer in the collective decay of various isomeric states of a molecule in an excited electronic state can be one of effective mechanisms of the photoisomerization of molecules whose structure is described by the model.     

On estimating probability of excited-state intramolecular proton transfer

Higher singlet states can play an important role in various intramolecular processes. Recent investigations of the time-resolved (with a picosecond resolution) spectra of the dual fluorescence of 3-hydroxyflavone molecules excited in the region of the S ₁ and S ₂ absorption bands by pulses with a duration of ∼44 ps have directly shown the occurrence of the proton transfer from the carboxyl to the carbonyl group of the molecule upon excitation into the second singlet absorption band. The reaction times estimated from the emission characteristics are comparable with the electronic level lifetime (several picoseconds), as a result of which the direct measurements are rather difficult. The proton transfer through the S ₂ state is also recorded in the steady-state fluorescence excitation spectra. In this study, it is shown how the reaction rate can be estimated from these data.     

Excited state intramolecular proton transfer in amino 2-(2′-hydroxyphenyl)benzazole derivatives: Effects of the solvent and the amino group position

The excited-state intramolecular proton transfer (ESIPT) mechanism in six amino 2-(2′-hydroxyphenyl)benzazole derivatives were investigated in different solvents by means of UV-vis absorption and steady-state fluorescence. The amino benzazoles are fluorescent in the blue-orange region under UV radiation. Changes in the absorption, emission and excitation spectra were analyzed and correlated to the position of the amino group and the solvent polarity. The equilibrium between the conformers in solution in the ground state, confirmed by the solvatochromic effect, reflects the dual fluorescence emission presented by these dyes.     

Direct photoexcitation of intramolecular proton transfer states in 3-hydroxyflavone

It is shown that the photoexcitation of 3-hydroxyflavone at the red edge of its absorption spectrum can directly excite luminescing intramolecular proton-transfer forms of molecules of this compound. This offers new possibilities for studying the fundamental properties of molecular objects with intramolecular proton transfer, which are currently considered as promising multiparametric molecular sensors.     

Excited state proton transfer and internal conversion in o-hydroxybenzaldehyde: new insights from non-adiabatic ab initio molecular dynamics

A recently developed non-adiabatic ab initio molecular dynamics method coupling the S₁ excited electronic state to the ground state by a surface hopping technique has been applied to study photoexcited o-hydroxybenzaldehyde. Vertical excitation of the enol tautomer to the π π* state leads to spontaneous proton transfer (PT) and thus formation of the keto tautomer. The PT process has been found to be entirely driven by the breathing mode of the H-chelate ring. In fact, there exists no barrier for PT in the S₁ state. Non-radiative decay of the π π* excited keto tautomer through internal conversion (IC) is observed on a picosecond time scale. The probability for a non-adiabatic surface hop from the S₁ state back to the ground state is seen to be correlated to the chelate ring breathing mode and to the temporal changes in the methoxy OH bond length. There are indications of an increased IC rate associated with the initial PT event.     

Photodynamics of intramolecular proton transfer in polar and nonpolar biflavonoid solutions

Using methods of steady state luminescence and femtosecond spectroscopy, we have studied the mechanism of intramolecular proton transfer in synthesized 3,7-dihydroxy-2,8-di(4-methoxyphenyl)-4H,6H-pyrano[3,2-g]chromen-4,6-dion in polar and nonpolar solutions, films, and polycrystals at 293 and 77 K. In an excited singlet state, intramolecular proton transfer occurs in two stages. At the first stage, a tautomer with one transferred proton (OTP tautomer) is formed from the Franck-Condon state within ??₁ = 0.6 ps. At the second stage, the second proton is transferred within ??₂ = 3.1 ps and a tautomer with two transferred protons (TTP tautomer) is formed, which fluoresces in toluene at 293 K with a high quantum yield, ?? _f = 0.66, and the fluorescence spectrum of which is characterized by a large Stokes shift, 9900 cm^?1. At 293 K, polar solvents (dimethylformamide, dimethyl sulfoxide, ethanol, etc.) solvate the BFV molecule in the ground state, while, in the excited state, an OTP tautomer is mainly formed. In polar ethanol at 77 K, a dual fluorescence spectrum is observed, which is caused by the fluorescence emission of polysolvates with ?? _max ^f = 460 nm and TTP phototautomers at ?? _max ^f = 610 nm.     

Manifestation of intramolecular proton transfer in imidazole in the electronic-vibrational spectrum

Electronic-vibrational spectra of both imidazole (I) and the intermediate molecular structure (II) in the intramolecular proton transfer process N₁H(I) → N₃H(III) have been calculated and analyzed theoretically. The geometries of the molecular structures of I and II in the first ππ* excited state were determined using semi-empirical correlations and the method of hybridized atomic orbitals. The difference in their spectra indicates that the intramolecular proton-transfer mechanism with imidazole (I ↔ III) tautomeric conversion can be identified by electronic-vibrational spectroscopy. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 2, pp. 164–169, March–April, 2008.     

Dye-laser pulse shortening by transient absorption following excited-state intramolecular proton transfer

Molecules undergoing excited-state intramolecular proton transfer often show transient absorption after pulsed optical excitation, due to the tautomeric form in the singlet ground state. This absorption may be used to suppress, after a short time, the laser action of dyes emitting in the transient absorption band. The method is designed for high photochemical stability. Lasing from PBBO, pumped 10 times above threshold by an excimer pumped PTP dye laser, was suppressed after 3.3ns by the addition of 2-(2-hydroxyphenyl)-benzoxazole, which absorbed 30% of the pump energy. At higher concentrations, intense and stable 80ps PBBO laser pulses were obtained. The pulse evolution is simulated by model calculations. A hypothetical super-dye, consisting of chemically linked laser- and absorber-moities, is also discussed. Here Förster energy transfer should result in particularly efficient laser pulse shortening.     

Computational prediction on photophysical properties of two excited state intramolecular proton transfer (ESIPT) fluorophores bearing the benzothiazole group

ABSTRACT

In this contribution, the photophysical properties of two excited state intramolecular proton transfer (ESIPT) fluorophores of 2,6-dibenzothiazolyl-4-methylphenol (I) and 2-benzothiazolyl-6-(2-(benzothiazolyl)vinyl)-4-methylphenol (II) were studied by density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods at the PBE0 theoretical level. To probe into the origin of the absorption and emission bands observed experimentally, the absorption and emission spectra of I and II were simulated by the TD-PBE0/6-311?+?G(d,p) calculations. In addition, the photo-induced proton enol–keto tautomerization of the two targeted molecules was also explored. The present studies indicate that a good agreement is found between theoretical predictions and experimental data. Moreover, both of these molecules can undergo an ultrafast ESIPT process, which should be responsible for the single proton-transfer tautomer emission.     

Fluorescence and excited state proton transfer of pyrene-3-carboxaldehyde

In very dilute water solutions, ca 10⁻⁷ M, pyrene-3-carboxaldehyde fluoresces with a high quantum yield, øF = 0.98. This emission is quenched at low pH and, if the proton activity is high enough, a new weak, red shifted fluorescence appears. These effects are explained by the existence of a fast proton transfer in the excited state. The emitting singlet is believed to be 6–7 orders of magnitude more basic than the ground electronic state. By measuring the changes in fluorescence intensity and lifetime of pyrene-3-carboxaldehyde as a function of pH, a value for the quenching rate constant k₂ = (2.2 ± 0.3) × 10¹⁰ M⁻¹ s⁻¹ was obtained. The quenching of the neutral form fluorescence is proposed to be produced by the protonation of the excited aldehyde, followed by a fast radiationless deactivation of the conjugated acid, before prototropic equilibrium can be attained.     

Excited state absorption and energy transfer losses in thulium doped fluoroindogallate glass

Thulium doped fluoroindogallate glass was characterized by means of excited state absorption experiment in the 0.95 to 1.55 μm spectral range. The three bands corresponding to the electronic transitions ³ F ₄→³ F ₂ (at 1.05 μm), ³ F ₄→³ F ₃ (at 1.125 μm), and ³ F ₄→³ H ₄ (at 1.45 μm) were observed. The energy transfer microscopic parameters for the reverse cross relaxation process ³ F ₄, ³ F ₄→³ H ₆, ³ H ₄ were calculated for different multipolar interaction mechanisms using the Kushida model, and it was verified that the probability of this process is 100 times lower than that of the direct ³ H ₄, ³ H ₆→³ F ₄, ³ F ₄ cross relaxation, responsible for the 1.8 μm emission pumping. PACS 78.20.-e; 78.55.Qr; 42.70.Hj; 42.55.Wd     

Ab initio investigation of excited state dual hydrogen bonding interactions and proton transfer mechanism for novel oxazoline compound

Owing to the importance of excited state dynamical relaxation, the excited state intramolecular proton transfer(ESIPT) mechanism for a novel compound containing dual hydrogen bond(abbreviated as "1-enol") is studied in this work.Using density functional theory(DFT) and time-dependent density functional theory(TDDFT) method, the experimental electronic spectra can be reproduced for 1-enol compound. We first verify the formation of dual intramolecular hydrogen bonds, and then confirm that the dual hydrogen bond should be strengthened in the first excited state. The photo-excitation process is analyzed by using frontier molecular orbital(HOMO and LUMO) for 1-enol compound. The obvious intramolecular charge transfer(ICT) provides the driving force to effectively facilitate the ESIPT process in the S1 state. Exploration of the constructed S0-state and S1-state potential energy surface(PES) reveals that only the excited state intramolecular single proton transfer occurs for 1-enol system, which makes up for the deficiencies in previous experiment.     

Experimental test of a four-level kinetic model for excited-state intramolecular proton transfer dye lasers

The nanosecond pulses of a dye laser oscillator based on the excited-state intramolecular proton-transfer reaction (IPT) of salicylamide and 2-hydroxylphenyl benzimidazole dyes have been studied as a function of several experimental parameters. To explain the operation of this laser a numerical four-level kinetic model was developed until the lasing properties of these dyes, in the presence of a variable oxygen concentration and pumped with a double pulse technique, could be reproduced. This was possible only by assuming that the efficiency of the laser is controlled by the absorption cross-section of a transient state with a lifetime in the nanosecond-picosecond range, which was tentatively identified as a ground state tautomeric species.     

Theoretical investigation on the excited state intramolecular proton transfer in Me_2N substituted flavonoid by the time-dependent density functional theory method

Time-dependent density functional theory(TDDFT) method is used to investigate the details of the excited state intramolecular proton transfer(ESIPT) process and the mechanism for temperature effect on the Enol*/Keto*emission ratio for the Me_2N-substited flavonoid(MNF) compound. The geometric structures of the S_0 and S_1 states are denoted as the Enol, Enol*, and Keto*. In addition, the absorption and fluorescence peaks are also calculated. It is noted that the calculated large Stokes shift is in good agreement with the experimental result. Furthermore, our results confirm that the ESIPT process happens upon photoexcitation, which is distinctly monitored by the formation and disappearance of the characteristic peaks of infrared(IR) spectra involved in the proton transfer and in the potential energy curves. Besides, the calculations of highest occupied molecular orbital(HOMO) and lowest unoccupied molecular orbital(LUMO) reveal that the electronegativity change of proton acceptor due to the intramolecular charge redistribution in the S_1 state induces the ESIPT. Moreover, the thermodynamic calculation for the MNF shows that the Enol*/Keto*emission ratio decreasing with temperature increasing arises from the barrier lowering of ESIPT.