Excited-state Proton Transfer Reaction Research Articles

Is it possible to switch ESIPT-channel of hydroxyanthraquinones with the strategy of modifying electronic groups?

In this work, to unveil the substituent effect on the excited-state intramolecular proton transfer (ESIPT) reaction of 1,8-Dihydroxyanthraquinone (DHAQ), four derivatives DHAQ-Me, DHAQ-NH2, DHAQ-COOH, and DHAQ-CN were considered using quantum chemistry methods in the acetonitrile (ACN) phase. The excited-state intramolecular hydrogen bonds (IHBs) (O1-H2⋯O3 and O5-H4⋯O3) strengthening mechanism was confirmed by computing primary geometric parameters, infrared (IR) spectra and reduced density gradient (RDG) scatter plots. The strength relationship of the dual IHBs within all the investigated compounds was established based on the calculated binding energies. Charge-recombination triggered ESIPT mechanism has been demonstrated by the analysis of frontier molecular orbitals (FMOs) and natural bond orbital (NBO) population. Besides, the hole-electron analysis indicates that a remarkable intramolecular charge transfer (ICT) behavior has induced the fluorescence intensity to decrease significantly for DHAQ-NH2 in K1 form. DHAQ derivatives with electron-withdrawing groups substituted (DHAQ-COOH and DHAQ-CN) have exhibited a larger Stokes shift, which is a desirable property for manufacturing luminescent materials. From the located transition state (TS) structures and the calculated potential energy curves (PECs), it is noticeable that the dominant channel for ESIPT reactions is always the O1-H2⋯O3 hydrogen bonding wire, which is irrelevant to the types of substituents introduced, although O5-H4⋯O3 is the stronger one for DHAQ-Me and DHAQ-NH2. This theoretical research may well deepen the comprehension of the relationship between IHB and ESIPT behavior and thereby provide valuable guidance to synthesize efficacious ESIPT-based organic chromophores experimentally.

Unveiling the influence of atomic electronegativity on the double ESIPT processes of uralenol: A theoretical study

In this work, the effects of atomic electronegativity (O, S, and Se atoms) on the competitive double excited-state intramolecular proton transfer (ESIPT) reactions and photophysical characteristics of uralenol (URA) were systematically explored by using the density functional theory (DFT) and time-dependent DFT (TD-DFT) methods. The calculated hydrogen bond parameters, infrared (IR) vibrational spectra, reduced density gradient (RDG) scatter plots, interaction region indicator (IRI) isosurface and topology parameters have confirmed the six-membered intramolecular hydrogen bond (IHB) O4H5…O3 is the stronger one in all the three studied compounds. Subsequently, frontier molecular orbitals (FMOs) and natural bond orbital (NBO) population analysis essentially uncover that the electron redistribution has induced the ESIPT process. Besides, the constructed potential energy curves (PECs) have indicated that the ESIPT process prefers to occur along the O4H5…O3 rather than the O1H2…O3 and the proton-transfer energy barrier is gradually decreased with the weakening of atomic electronegativity from URA to URA-S and URA-Se. In a conclusion, the attenuating of atomic electronegativity has enhanced the IHBs of URA and thereby promoting the ESIPT reaction, which is helpful for further developing novel fluorophores based on ESIPT behavior in the future.

Nonadiabatic quantum dynamics of the coherent excited state intramolecular proton transfer of 10-hydroxybenzo[h]quinoline

The photoinduced nonadiabatic dynamics of the enol-keto isomerization of 10-hydroxybenzo[h]quinoline (HBQ) are studied computationally using high-dimensional quantum dynamics. The simulations are based on a diabatic vibronic coupling Hamiltonian, which includes the two lowest pi pi ^* excited states and a npi ^* state, which has high energy in the Franck–Condon zone, but significantly stabilizes upon excited state intramolecular proton transfer. A procedure, applicable to large classes of excited state proton transfer reactions, is presented to parametrize this model using potential energies, forces and force constants, which, in this case, are obtained by time-dependent density functional theory. The wave packet calculations predict a time scale of 10–15 fs for the photoreaction, and reproduce the time constants and the coherent oscillations observed in time-resolved spectroscopic studies performed on HBQ. In contrast to the interpretation given to the most recent experiments, it is found that the reaction initiated by 1pi pi ^* longleftarrow S_0 photoexcitation proceeds essentially on a single potential energy surface, and the observed coherences bear signatures of Duschinsky mode-mixing along the reaction path. The dynamics after the 2pi pi ^* longleftarrow S_0 excitation are instead nonadiabatic, and the npi ^* state plays a major role in the relaxation process. The simulations suggest a mainly active role of the proton in the isomerization, rather than a passive migration assisted by the vibrations of the benzoquinoline backbone.Graphic

Solvent Effect on Excited-State Intramolecular Proton-Coupled Charge Transfer Reaction in Two Seven-Membered Ring Pyrrole-Indole Hydrogen Bond Systems

In the past decades, tremendous efforts have been invested into organic molecules involved in the excited-state intramolecular proton transfer (ESIPT) reaction due to their enormously Stokes-shifted fluorescence and distinctive photophysical properties. The alterations of the environmental medium can effectively adjust the luminous performance of ESIPT molecules, which inspires us to unravel the solvent effect on the ESIPT mechanism. Here, we report the solvent-dependent excited-state properties of two new seven-membered ring pyrrole-indole ESIPT molecules, g-PPDBI and e-PPDBI, by steady-state spectra, picosecond transient fluorescence spectra, femtosecond transient absorption spectra, and theoretical calculations. The bathochromic-shifted normal fluorescence and the negligibly shifted tautomer fluorescence suggest the occurrence of an excited-state intramolecular proton-coupled charge transfer reaction. Thus, the solvent effect plays a vital role in stabilizing the intramolecular charge transferred state, resulting in a higher ESIPT reaction barrier in more polar solvents. Additionally, the observation of the slight dynamic difference between PPDBIs with different π-conjugation positions provides a new strategy to adjust the performance of ESIPT molecules.

Structural Origin and Vibrational Fingerprints of the Ultrafast Excited State Proton Transfer of the Pyranine-Acetate Complex in Aqueous Solution.

The excited state proton transfer (ESPT) reaction from the photoacid 8-hydroxypyrene-1,3,6-trisulfonic acid (HPTS or pyranine) to an acetate molecule has been investigated in explicit aqueous solution via excited state ab initio molecular dynamics simulations based on hybrid quantum/molecular mechanics (QM/MM) potentials. In all the trajectories, the direct proton transfer has been observed in the excited state within 1 ps. We find that the initial structural configuration extracted from the ground state distribution strongly affects the ESPT kinetics. Indeed, the relative orientation of the proton donor-acceptor pair and the presence of a water molecule hydrogen bonded to the phenolic acid group of the pyranine are the key factors to facilitate the ESPT. Furthermore, we analyze the vibrational fingerprints of the ESPT reaction, reproducing the blue shift of the acetate CO stretching (COac), from 1666 to 1763 cm-1 testifying the transformation of acetate to acetic acid. Finally, our findings suggest that the acetate CC stretching (CCac) is also sensitive to the progress of the ESPT reaction. The CCac stretching is indeed ruled by the two vibrational modes (928 and 1426 cm-1), that in the excited state are alternately activated when the proton is shared or bound to the donor/acceptor, respectively.

In silico simulation of the excited state proton transfer reaction of 2-(2-furyl)-3-hydroxychromone (FHC) in solution by empirical valence bond (EVB) method in conjunction with classical molecular dynamics

2-(2-Furyl)-3-hydroxychromone (FHC) is a dual emitter fluorescent probe exhibiting excited state intramolecular proton transfer (ESIPT) reaction in solution and inserted in biological relevant macromolecules. Its two fluorescence bands are attributed to normal form (N*) for the short wavelength and the long-wavelength band to the tautomer form (T*), the product of the ESIPT reaction. To rationalise the mechanisms that lead to the occurrence of the ESIPT reaction and predict the fluorescence spectra, the excited and ground state dynamic of this compound was followed in acetonitrile, ethanol, methanol, N-methylformamide and formamide, by the classical molecular dynamic simulation in conjunction with the empirical valence bond (EVB) model to describe bond dissociation process. A set of transferable parameters were used to fit the EVB potential energy curve to TDDFT data. Using these parameters, the occurrence time of the ESIPT reaction was predicted to be 7, 84, 113, 98, 207ps, respectively in the considered solvents, in excellent agreement with the experimentally reported values. These values are comparatively higher than those determined for the parent flavone dye (less than 100 fs), giving FHC a higher potential for sensor development. By examining structural parameters such as the distance from the proton to acceptor, the intermolecular H-bond between FHC and the solvent molecules and proton trajectories, we found that ESIPT occured in acetonitrile and alcohols as a combination of low frequency high amplitude donor-acceptor bending motion and charge redistribution in the excited state, that were modulated by the solvent H-bond donor potency. Differently in amides ESIPT occured via tunnelling mechanism due to the close energy of N* and T*. Fluorescence spectra calculated from potential energies of the EVB model along the reaction coordinates were qualitatively in agreement with the recorded spectra.

Chapter Open for the Excited-State Intramolecular Thiol Proton Transfer in the Room-Temperature Solution.

We report here, for the first time, the experimental observation on the excited-state intramolecular proton transfer (ESIPT) reaction of the thiol proton in room-temperature solution. This phenomenon is demonstrated by a derivative of 3-thiolflavone (3TF), namely, 2-(4-(diethylamino)phenyl)-3-mercapto-4H-chromen-4-one (3NTF), which possesses an -S-H···O═ intramolecular H-bond (denoted by the dashed line) and has an S1 absorption at 383 nm. Upon photoexcitation, 3NTF exhibits a distinctly red emission maximized at 710 nm in cyclohexane with an anomalously large Stokes shift of 12 230 cm-1. Upon methylation on the thiol group, 3MeNTF, lacking the thiol proton, exhibits a normal Stokes-shifted emission at 472 nm. These, in combination with the computational approaches, lead to the conclusion of thiol-type ESIPT unambiguously. Further time-resolved study renders an unresolvable (<180 fs) ESIPT rate for 3NTF, followed by a tautomer emission lifetime of 120 ps. In sharp contrast to 3NTF, both 3TF and 3-mercapto-2-(4-(trifluoromethyl)phenyl)-4H-chromen-4-one (3FTF) are non-emissive. Detailed computational approaches indicate that all studied thiols undergo thermally favorable ESIPT. However, once forming the proton-transferred tautomer, the lone-pair electrons on the sulfur atom brings non-negligible nπ* contribution to the S1' state (prime indicates the proton-transferred tautomer), for which the relaxation is dominated by the non-radiative deactivation. For 3NTF, the extension of π-electron delocalization by the diethylamino electron-donating group endows the S1' state primarily in the ππ* configuration, exhibiting the prominent tautomer emission. The results open a new chapter in the field of ESIPT, covering the non-canonical sulfur intramolecular H-bond and its associated ESIPT at ambient temperature.

Substituents effect on the methanol-assisted excited-state intermolecular proton transfer of 7-Aminoquinoline: A theoretical study

Studies have shown that changing the substituted groups applied to the amine can effectively affect the strength of the excited state hydrogen bond. However, it is not common to study the mechanism of how to effectively control the hydrogen bond strength of the excited state through the substituted group. Here, we have taken 7-Aminoquinoline and its various derivatives, the TDDFT method is used to study the influence of its R substitution on the hydrogen bond strength of the excited state and the mechanism of solvent-assisted excited-state multiple proton transfer (ESMPT) reaction. We have utilized bond length, IR vibrational spectra, atomic polar tensors (APT) charge analysis and potential energy curves to depict the relationship between hydrogen bond strength and substituted groups in excited state. We have modulated deliberately the number of methanol molecules involved in the ESMPT processes based on the site-specificity of hydrogen-bonding interactions, the potential energy curves indicate that the proton transfer process is more likely to happen in 7AQs·(MeOH)3 tetramer than in 7AQs·(MeOH)2 trimer, which is conflict with previous experimental conclusion. Meanwhile, the transition state structure during the ESMPT reaction indicates that the process is concerted. Our study demonstrates well the fluorescence behavior of 7AQs molecules regulated by different R substituents and extends the boundaries of site-specific hydrogen-bonding interactions research slightly.

Photoinduced Generation of the π-Conjugated Zwitterionic State in the ESIPT Fluorophore of 2,4-Bisimidazolylphenol

We demonstrate that 2,4-bis(4,5-diphenyl-1H-imidazol-2-yl)phenol (2,4-bImP) undergoes photoinduced conversion into the so-called "π-conjugated zwitterion" after causing an excited-state intramolecular proton transfer (ESIPT) reaction. The powder sample of 2,4-bImP exhibits largely Stokes-shifted fluorescence characteristics to ESIPT fluorophores. On the other hand, its originally colorless solutions become colored when exposed to UV light for several minutes, whose color depends on the type of solvent. In particular, the CHCl3 solution rapidly turns dark green with the absorption maximum around 700 nm, and the colored solution is nearly restored to original by alternating addition of acid and base. To explain such drastic and reversible color changes, we hypothesized that the occurrence of ESIPT (i.e., deprotonation of the phenol and protonation of the imidazolyl group at its 2-position) triggered the charge-separated structure between the negatively charged phenolate and the positively charged imidazoliumyl group at its 4-position, which allowed resonance with the neutral p-quinoid structure. The formation of this π-conjugated zwitterion was strongly supported by the results of 1H and 15N NMR and Raman measurements.

Excited-State Intramolecular Proton Transfer Reaction and Ground-State Hole Dynamics of 4'-N,N-Dialkylamino-3-hydroxyflavone in Ionic Liquids Studied by Transient Absorption Spectroscopy.

The excited-state intramolecular proton transfer (ESIPT) of 4'-N,N-dialkylamino-3-hydroxyflavone (CnHF) having different alkyl chain lengths (ethyl, butyl, and octyl chains) was investigated in ionic liquids (ILs) by steady-state fluorescence and transient absorption spectroscopy. Upon photoexcitation, CnHF underwent ESIPT from the normal form to the tautomer form, and dual emissions from both states were detected. For C4HF and C8HF, the tautomerization yields determined from the fluorescence intensity ratios increased with the increasing number of alkyl chain carbon atoms in the cation and on reducing the excitation wavelength as reported for C2HF [K. Suda et al., J. Phys. Chem. B. 117, 12567 (2013)]. The transient absorption spectra of CnHF were measured at excitation wavelengths of 360, 400, and 450 nm. The ESIPT rate determined from the induced emission of the tautomer was correlated with the tautomerization yield for C2HF and C4HF. In addition, the recovery of the ground-state bleach was found to be strongly dependent on the excitation wavelength. This result indicates that the solvated state of the molecule before photoexcitation is dependent on the excitation wavelengths. The time constant for the ground-state relaxation was slower than that for the excited state.

Water-Mediated Excited State Proton Transfer of Pyranine-Acetate in Aqueous Solution: Vibrational Fingerprints from Ab Initio Molecular Dynamics.

In this work, we simulate the excited state proton transfer (ESPT) reaction involving the pyranine photoacid and an acetate molecule as proton acceptor, connected by a bridge water molecule. We employ ab initio molecular dynamics combined with an hybrid quantum/molecular mechanics (QM/MM) framework. Furthermore, a time-resolved vibrational analysis based on the wavelet-transform allows one to identify two low frequency vibrational modes that are fingerprints of the ESPT event: a ring wagging and ring breathing. Their composition suggests their key role in optimizing the structure of the proton donor–acceptor couple and promoting the ESPT event. We find that the choice of the QM/MM partition dramatically affects the photoinduced reactivity of the system. The QM subspace was gradually extended including the water molecules directly interacting with the pyranine–water–acetate system. Indeed, the ESPT reaction takes place when the hydrogen bond network around the reactive system is taken into account at full QM level.

Substituent Effects on Excited-State Intramolecular Proton Transfer Reaction of 2-Aryloxazoline Derivatives

Different substituents and benzene ring numbers had significant effects on the fluorescence phenomenon of 2-aryloxazoline derivatives as observed in an experiment. Here, we select five 2-aryloxazoline derivatives with different substituents and benzene ring numbers (2u, 2ad, 2af, 2ai, and 2ah) to analyze the effects on the fluorescence phenomena. For 2ad, 2ah, and 2ai, first, the geometric structures are optimized based on the density functional theory and time-dependent density functional theory methods. The analysis of the obtained bond parameters reveals the variation of hydrogen bond interactions from S0 to S1 states. Second, the calculated absorption and emission spectra are consistent with the experimental values, which proves that the theoretical method is feasible. Finally, through the analysis of the infrared vibrational spectrum, reduced density gradient isosurfaces, frontier molecular orbitals, and potential energy curves, the strengthening mechanism of the hydrogen bond interaction and the ability of the excited-state intramolecular proton transfer (ESIPT) reaction to occur are further explained. Since the proton transfer reactions of 2u and 2af occur spontaneously under photoexcitation, they have no stable structures in the S1 state. In conclusion, due to the different substituents, 2u is more prone to the proton transfer reaction than 2ad. For 2af, 2ai, and 2ah with different benzene ring numbers, the ESIPT reaction is more difficult to occur as the number of benzene rings increases. The ability of the ESIPT reaction to occur follows the order 2af → 2ah → 2ai. For 2-aryloxazoline derivatives with different substituents or different benzene ring numbers, the hydrogen bond strengthening mechanism has been authenticated, which promotes the occurrence of the ESIPT reactions.

Opposite substituent effects in the ground and excited states on the acidity of N-H fragments involved in proton transfer reaction in aromatic urea compounds.

To investigate substitution effects on excited-state intermolecular proton transfer (ESPT) reactions as well as acidity of proton donating fragments in the ground state, we synthesized substituted anthracen-2-yl-3-phenylurea derivatives that form a hydrogen bonds with acetate anions and undergo ESPT reaction. Fluorescence lifetime measurements and their kinetic analyses revealed that the trifluoromethyl group on the phenyl ring as an electron-withdrawing group caused a slow ESPT reaction despite an increase in the acidity of the N-H fragment in the ground state. In contrast, the methoxy group as a donating group leads to a fast ESPT reaction despite a reduction of the acidity of the N-H fragment in the ground state. These effects of substituents on ESPT reaction are due to their influence on the charge transfer reaction, which occurs from the N-H fragment to the anthryl ring to increase the acidity of N-H followed by ESPT reaction, over the urea unit by a combination of resonance and inductive effects. These opposing effects of substituents on the acidity of the urea unit in the ground and excited states provide an important insight in balancing the reactivity of proton transfer reaction in both the excited and ground states.

Ultrafast Dynamics and Photoresponse of a Fungi-Derived Pigment Xylindein from Solution to Thin Films.

Organic semiconductor materials have recently gained momentum due to their non-toxicity, low cost, and sustainability. Xylindein is a remarkably photostable pigment secreted by fungi that grow on decaying wood, and its relatively strong electronic performance is enabled by π-π stacking and hydrogen-bonding network that promote charge transport. Herein, femtosecond transient absorption spectroscopy with a near-IR probe was used to unveil a rapid excited-state intramolecular proton transfer reaction. Conformational motions potentially lead to a conical intersection that quenches fluorescence in the monomeric state. In concentrated solutions, nascent aggregates exhibit a faster excited state lifetime due to excimer formation, confirmed by the excimer→charge-transfer excited-state absorption band of the xylindein thin film, thus limiting its optoelectronic performance. Therefore, extending the xylindein sidechains with branched alkyl groups may hinder the excimer formation and improve optoelectronic properties of naturally derived materials.

Effect of Water Microsolvation on the Excited-State Proton Transfer of 3-Hydroxyflavone Enclosed in γ-Cyclodextrin.

The effect of microsolvation on excited-state proton transfer (ESPT) reaction of 3-hydroxyflavone (3HF) and its inclusion complex with γ-cyclodextrin (γ-CD) was studied using computational approaches. From molecular dynamics simulations, two possible inclusion complexes formed by the chromone ring (C-ring, Form I) and the phenyl ring (P-ring, Form II) of 3HF insertion to γ-CD were observed. Form II is likely more stable because of lower fluctuation of 3HF inside the hydrophobic cavity and lower water accessibility to the encapsulated 3HF. Next, the conformation analysis of these models in the ground (S0) and the first excited (S1) states was carried out by density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations, respectively, to reveal the photophysical properties of 3HF influenced by the γ-CD. The results show that the intermolecular hydrogen bonding (interHB) between 3HF and γ-CD, and intramolecular hydrogen bonding (intraHB) within 3HF are strengthened in the S1 state confirmed by the shorter interHB and intraHB distances and the red-shift of O–H vibrational modes involving in the ESPT process. The simulated absorption and emission spectra are in good agreement with the experimental data. Significantly, in the S1 state, the keto form of 3HF is stabilized by γ-CD, explaining the increased quantum yield of keto emission of 3HF when complexing with γ-CD in the experiment. In the other word, ESPT of 3HF is more favorable in the γ-CD hydrophobic cavity than in aqueous solution.

Harnessing Excited-State Proton Transfer Reaction for 2-(6'-Hydroxy-2'-pyridyl)benzimidazole via Solvents.

2-(6'-Hydroxy-2'-pyridyl)benzimidazole (BI), having double functional groups donating protons, is investigated theoretically with an aim to determine the excited-state proton transfer (ESPT) mechanism in different solvents. We demonstrate that the ESPT reaction can take place with the assistance of protic solvents (water and ethanol). At the same time, the vitally important role of bridges of water and ethanol for the ESPT reaction is confirmed by the disappearance of the ESPT reaction when we replaced the protic solvent with aprotic solvent acetonitrile (ACN). We regulate the ESPT reaction of BI via solvents successfully. A different ESPT mechanism from the one proposed previously (the proton of BI transfers from benzimidazole NH to pyridyl nitrogen in ethanol) is proposed. Our simulated potential energy barriers indicate that the ESPT reaction of BI can occur only between the hydroxyl proton and pyridyl nitrogen with the assistance of water or ethanol molecules. We further verify that the water- or ethanol-assisted ESPT reaction of BI is stepwise, and the concerted mechanism is unambiguously ruled out. This systematic investigation into the ESPT mechanism of BI is significant in designing and constructing the desirable supramolecular architectures, which can provide potential supramolecular recognition sites and supramolecular inter- or intra-H-bonding interactions.

Excited-state intramolecular proton transfer with and without the assistance of vibronic-transition-induced skeletal deformation in phenol-quinoline.

The excited-state intramolecular proton transfer (ESIPT) reaction of two phenol–quinoline molecules (namely PQ-1 and PQ-2) were investigated using time-dependent density functional theory. The five-(six-) membered-ring carbocycle between the phenol and quinolone moieties in PQ-1 (PQ-2) actually causes a relatively loose (tight) hydrogen bond, which results in a small-barrier (barrier-less) on an excited-state potential energy surface with a slow (fast) ESIPT process with (without) involving the skeletal deformation motion up to the electronic excitation. The skeletal deformation motion that is induced from the largest vibronic excitation with low frequency can assist in decreasing the donor–acceptor distance and lowering the reaction barrier in the excited-state potential energy surface, and thus effectively enhance the ESIPT reaction for PQ-1. The Franck–Condon simulation indicated that the low-frequency mode with vibronic excitation 0 → 1′ is an original source of the skeletal deformation vibration. The present simulation presents physical insights for phenol–quinoline molecules in which relatively tight or loose hydrogen bonds can influence the ESIPT reaction process with and without the assistance of the skeletal deformation motion.

Intermolecular Hydrogen Bonding Tunes Vibronic Coupling in Heptazine Complexes.

To better understand how hydrogen bonding influences the excited-state landscapes of aza-aromatic materials, we studied hydrogen-bonded complexes of 2,5,8-tris (4-methoxyphenyl)-1,3,4,6,7,9,9b-heptaazaphenalene (TAHz), a molecular photocatalyst related to graphitic carbon nitride, with a variety of phenol derivatives (R-PhOH). By varying the electron-withdrawing character of the para-substituent on the phenol, we can modulate the strength of the hydrogen bond. Using time-resolved photoluminescence, we extract a spectral component associated with the R-PhOH-TAHz hydrogen-bonded complex. Surprisingly, we noticed a striking change in the relative amplitude of vibronic peaks in the TAHz-centered emission as a function of R-group on phenol. To gain a physical understanding of these spectral changes, we employed a displaced-oscillator model of molecular emission to fit these spectra. This fit assumes that two vibrational modes are dominantly coupled to the emissive electronic transition and extracts their frequencies and relative nuclear displacements (related to the Huang-Rhys factor). With the aid of quantum chemical calculations, we found that heptazine ring-breathing and ring-puckering modes are likely responsible for the observed vibronic progression, and both modes indicate decreasing molecular distortion in the excited state with increasing hydrogen bond strength. This finding offers new insights into intermolecular excited-state hydrogen bonding, which is a crucial step toward controlling excited-state proton-coupled electron transfer and proton transfer reactions.

Modeling Excited-State Proton Transfer to Solvent: A Dynamics Study of a Super Photoacid with a Hybrid Implicit/Explicit Solvent Model.

The rapid growth of time-resolved spectroscopies and the theoretical advances in ab initio molecular dynamics (AIMD) pave the way to look at the real-time molecular motion following the electronic excitation. Here, we exploited the capabilities of AIMD combined with a hybrid implicit/explicit model of solvation to investigate the ultrafast excited-state proton transfer (ESPT) reaction of a super photoacid, known as QCy9, in water solution. QCy9 transfers a proton to a water solvent molecule within 100 fs upon the electronic excitation in aqueous solution, and it is the strongest photoacid reported in the literature so far. Because of the ultrafast kinetics, it has been experimentally hypothesized that the ESPT escapes the solvent dynamics control (Huppert et al., J. Photochem. Photobiol. A2014,277, 90). The sampling of the solvent configuration space on the ground electronic state is the first key step toward the simulation of the ESPT event. Therefore, several configurations in the Franck–Condon region, describing an average solvation, were chosen as starting points for the excited-state dynamics. In all cases, the excited-state evolution spontaneously leads to the proton transfer event, whose rate is strongly dependent on the hydrogen bond network around the proton acceptor solvent molecule. Our study revealed that the explicit representation at least of three solvation shells around the proton acceptor molecule is necessary to stabilize the excess proton. Furthermore, the analysis of the solvent molecule motions in proximity of the reaction site suggested that even in the case of the strongest photoacid, the ESPT is actually assisted by the solvation dynamics of the first and second solvation shells of the water accepting molecule.

4’-Nitroflavonol fluorescence: Excited state intramolecular proton transfer reaction from the non-emissive excited state

2-(4′-nitrophenyl)-3-hydroxy-chromone (4′-nitroflavonol, NO3 H F), which can be considered as non-typical representative of fluorescent dyes of flavonol series, was synthesized. Its spectral and photophysical properties were studied experimentally and modeled with several relevant quantum-chemical approaches. Single banded, long-wavelength highly Stokes shifted fluorescence phototautomer emission was observed for the title compound in solvents of different polarity. Absence of its short-wavelength “normal” emission band was explained by the effect of ultrafast intersystem crossing (ISC) with participation of triplet nπ* levels of 4′-nitro group. Such behavior, absence of fluorescence emission below ∼500 nm is generally expected for nitro-aromatics. Thus, a rare example of excited state intramolecular proton transfer reaction (ESIPT) originated from the non-emissive “dark” excited state at conditions of its concurrence with ultrafast ISC should be considered for the title compound. Excited state proton transfer reaction plays in this case the role of an emission regulating factor: the higher is its rate, the more intensive phototautomer fluorescence is observed. Relatively long fluorescence lifetimes of 4′-nitroflavonol in solvents of intermediate polarity (∼ 4 ns) were attributed to low efficiency of radiationless processes in its phototautomer form.