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.     

A theoretical assignment on excited‐state intramolecular proton transfer mechanism for quercetin

In the present work, we investigate a new chromophore (ie, quercetin) (Simkovitch et al J Phys Chem B 119 [2015] 10244) about its complex excited‐state intramolecular proton transfer (ESIPT) process based on density functional theory and time‐dependent density functional theory methods. On the basis of the calculation of electron density ρ( r ) and Laplacian ?²ρ( r ) at the bond critical point using atoms‐in‐molecule theory, the intramolecular hydrogen bonds (O₁‐H₂?O₅ and O₃‐H₄?O₅) have been supported to be formed in the S₀ state. Comparing the prime structural variations of quercetin involved in its 2 intramolecular hydrogen bonds, we find that these 2 hydrogen bonds should be strengthened in the S₁ state, which is a fundamental precondition for facilitating the ESIPT process. Concomitantly, infrared vibrational spectra analysis further verifies this viewpoint. In good agreement with previous experimental spectra results, we find that quercetin reveals 2 kinds of excited‐state structures (quercetin* and quercetin‐PT1*) in the S₁ state. Frontier molecular orbitals depict the nature of electronically excited state and support the ESIPT reaction. Our scanned potential energy curves according to variational O₁‐H₂ and O₃‐H₄ coordinates demonstrate that the proton transfer process should be more likely to occur in the S₁ state via hydrogen bond wire O₁‐H₂?O₅ rather than O₃‐H₄?O₅ because of the lower potential energy barrier 2.3 kcal/mol. Our present work explains previous experimental result and makes up the deficiency of mechanism in previous experiment. In the end, we make a reasonable assignment for ESIPT process of quercetin.     

激发态分子内质子转移有机分子HBT的三阶非线性光学特性

以532nm皮秒脉冲作抽运光,采用单光束Z-扫描技术对具有激发态分子内质子转移效应的有机分子2-(2′-羟基苯基)苯并噻唑(HBT)在其双光子吸收区的非线性光学特性进行了研究.实验结果表明,对532nm波长的光,HBT分子存在明显的双光子吸收.通过拟合开孔Z-扫描实验数据,求解了HBT分子在其双光子吸收区的非线性吸收系数,并探讨了抽运光强度对介质双光子吸收效应的影响.采用高斯分解法,通过拟合闭孔Z-扫描除以开孔Z-扫描数据,理论推导并计算了在介质对抽运光存在非线性吸收的情况下HBT分子的非线性折射率,以及不同入射光强度时HBT分子的三阶非线性极化率实部和虚部的值.计算结果表明,理论分析与实验结果较好地符合,这些结果为进一步研究和开发此类材料的应用提供了理论与实验依据.     

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.     

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.     

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.     

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.     

Theoretical investigation on the excited state intramolecular proton coupled charge transfer phenomenon for a novel fluorophore

We theoretically investigate the excited state behaviors of the novel fluorophore tetraphenylethene‐2‐(2′‐hydroxyphenyl)benzothiazole (TPE‐HBT), which was designed based on the intersection of TPE and HBT, using density functional theory and time‐dependent density functional theory methods. Compared with previous experimental results about fluorescence peaks, our calculated results are in good agreement with experimental data, which further confirms that the theoretical level we used is reasonable. Furthermore, our results confirm that the excited state intramolecular proton transfer (ESIPT) process happens upon photoexcitation, which is distinctly monitored by the infrared spectra and the potential energy curves. In addition, the calculation of highest occupied molecular orbital and lowest unoccupied molecular orbital reveals that the electron density change of proton acceptor because of the intramolecular charge transfer (ICT) process in the S₁ state induces the ESIPT. Moreover, the transition density matrix is worked out to facilitate deeper insight into the ESIPT coupled ICT process. It is hoped that the present work not only elaborates the ESIPT coupled ICT phenomenon and corresponding mechanisms for the TPE‐HBT but also may be helpful to design and develop new materials and applications involved in TPE‐HBT systems in future.     

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.     

10-羟基苯并喹啉激发态分子内质子转移取代基效应的理论研究

运用密度泛函(DFT)和含时密度泛函(TDDFT)计算方法研究了10-羟基苯并喹啉(HBQ)及其衍生物分子内质子转移过程,探究了取代基效应对质子转移过程的影响,研究发现,HBQ及其衍生物可以形成分子内氢键,且激发态时氢键增强.基态时各分子以醇式构型稳定存在,激发态时酮式构型为优势构象.各化合物的最大吸收峰和发射峰主要是电子从HOMO到LUMO之间的跃迁引起的.基态分子内质子转移(醇式→酮式)需要跃过较高的能垒因而难以发生,而激发态时只需跃过较低能垒就很容易发生分子内质子转移,吸电子基的引入可以使该过程的能垒降低,因此吸电子基有利于激发态质子转移.取代基效应影响化合物的光谱性质.     

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.     

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.