Tautomer Emission Research Articles

Structural tuning intra- versus inter-molecular proton transfer reaction in the excited state

A series of 2-pyridyl-pyrazole derivatives 1-4 possessing five-membered ring hydrogen bonding configuration are synthesized, the structural flexibility of which is strategically tuned to be in the order of 1 > 2 > 3 > 4. This system then serves as an ideal chemical model to investigate the correlation between excited-state intramolecular proton transfer (ESIPT) reaction and molecular skeleton motion associated with hydrogen bonds. The resulting luminescence data reveal that the rate of ESIPT decreases upon increasing the structural constraint. At sufficiently low concentration where negligible dimerization is observed, ESIPT takes place in 1 and 2 but is prohibited in 3 and 4, for which high geometry constraint is imposed. The results imply that certain structural bending motions associated with hydrogen bonding angle/distance play a key role in ESIPT. This trend is also well supported by the DFT computational approach, in which the barrier associated with ESIPT is in the order of 1 < 2 < 3 < 4. Upon increasing the concentration in cyclohexane, except for 2, the rest of the title compounds undergo ground-state dimerization, from which the double proton transfer takes place in the excited state, resulting in a relatively blue shifted dimeric tautomer emission (cf. the monomer tautomer emission). The lack of dimerization in 2 is rationalized by substantial energy required to adjust the angle of hydrogen bond via twisting the propylene bridge prior to dimerization.

Ab initio study of the solvent H-bonding effect on ESIPT reaction and electronic transitions of 3-hydroxychromone derivatives

The electronic transitions occurring in 4-(N,N-dimethylamino)-3-hydroxyflavone (DMAF) and 2-furanyl-3-hydroxychromone (FHC) were investigated using the TDDFT method in aprotic and protic solvents. The solvent effect was incorporated into the calculations via the PCM formalism. The H-bonding between solute and protic solvent was taken into account by considering a molecular complex between these molecules. To examine the effect of the H-bond on the ESIPT reaction, the absorption and emission wavelengths as well as the energies of the different states that intervene during these electronic transitions were calculated in acetonitrile, ethanol and methanol. The calculated positions of the absorption and emission wavelengths in various solvents were in excellent agreement with the experimental spectra, validating our approach. We found that in DMAF, the hydrogen bonding with protic solvents makes the ESIPT reaction energetically unfavourable, which explains the absence of the ESIPT tautomer emission in protic solvents. In contrast, the excited tautomer state of FHC remains energetically favourable in both aprotic and protic solvents. Comparing our calculations with the previously reported time-resolved fluorescence data, the ESIPT reaction of DMAF in aprotic solvents is reversible because the emitting states are energetically close, whereas in FHC, ESIPT is irreversible because the tautomer state is below the corresponding normal state. Therefore, the ESIPT reaction in DMAF is controlled by the relative energies of the excited states (thermodynamic control), while in FHC the ESIPT is controlled probably by the energetic barrier (kinetic control).

A Genuine Intramolecular Proton Relay System Undergoing Excited-State Double Proton Transfer Reaction

7-Hydroxyquinoline-8-carboxylic acid (1), which possesses dual intramolecular hydrogen bonds, undergoes excited-state intramolecular double proton transfer, (ESIDPT) resulting in a quinolinone-like tautomer emission (λmax ∼ 470 nm). ESIDPT of 1 is cooperative, as evidenced by chemically blocking either proton donating site. While the overall rate of ESIDPT is higher than the system response limit, (220 fs)–1, the theoretical approach favors a concerted, asynchronous ESIDPT with a rather small or negligible barrier, demonstrating an intrinsic proton relay system that undergoes intramolecular double proton transfer in the electronic excited state.

Fine Tuning the Energetics of Excited-State Intramolecular Proton Transfer (ESIPT): White Light Generation in A Single ESIPT System

Using 7-hydroxy-1-indanone as a prototype (I), which exhibits excited-state intramolecular proton transfer (ESIPT), chemical modification has been performed at C(2)-C(3) positions by fusing benzene (molecule II) and naphthalene rings, (molecule III). I undergoes an ultrafast rate of ESIPT, resulting in a unique tautomer emission (λ(max) ∼530 nm), whereas excited-state equilibrium is established for both II and III, as supported by the dual emission and the associated relaxation dynamics. The forward ESIPT (normal to proton-transfer tautomer species) rates for II and III are deduced to be (30 ps)(-1) and (22 ps)(-1), respectively, while the backward ESIPT rates are (11 ps)(-1) and (48 ps)(-1). The ESIPT equilibrium constants are thus calculated to be 0.37 and 2.2 for II and III, respectively, giving a corresponding free energy change of 0.59 and -0.47 kcal/mol between normal and tautomer species. For III, normal and tautomer emissions in solid are maximized at 435 and 580 nm, respectively, achieving a white light generation with Commission Internationale de l'Eclairage (CIE) (0.30, 0.27). An organic light-emitting diode based on III is also successfully fabricated with maximum brightness of 665 cd m(-2) at 20 V (885 mA cm(-2)) and the CIE coordinates of (0.26, 0.35). The results provide the proof of concept that the white light generation can be achieved in a single ESIPT system.

Excited-State Intramolecular Proton Transfer Molecules Bearing o-Hydroxy Analogues of Green Fluorescent Protein Chromophore

o-Hydroxy analogues, 1a-g, of the green fluorescent protein chromophore have been synthesized. Their structures and electronic properties were investigated by X-ray single-crystal analyses, electrochemistry, and luminescence properties. In solid and nonpolar solvents 1a-g exist mainly as Z conformers that possess a seven-membered-ring hydrogen bond and undergo excited-state intramolecular proton transfer (ESIPT) reactions, resulting in a proton-transfer tautomer emission. Fluorescence upconversion dynamics have revealed a coherent type of ESIPT, followed by a fast vibrational/solvent relaxation (<1 ps) to a twisted (regarding exo-C(5)-C(4)-C(3) bonds) conformation, from which a fast population decay of a few to several tens of picoseconds was resolved in cyclohexane. Accordingly, the proton-transfer tautomer emission intensity is moderate (0.08 in 1e) to weak (∼10(-4) in 1a) in cyclohexane. The stronger intramolecular hydrogen bonding in 1g suppresses the rotation of the aryl-alkene bond, resulting in a high yield of tautomer emission (Φ(f) ≈ 0.2). In the solid state, due to the inhibition of exo-C(5)-C(4)-C(3) rotation, intense tautomer emission with a quantum yield of 0.1-0.9 was obtained for 1a-g. Depending on the electronic donor or acceptor strength of the substituent in either the HOMO or LUMO site, a broad tuning range of the emission from 560 (1g) to 670 nm (1a) has been achieved.

En Route to White-Light Generation Utilizing Nanocomposites Composed of Ultrasmall CdSe Nanodots and Excited-State Intramolecular Proton Transfer Dyes

One single material that emits white light is of paramount interest for the development of white light-emitting diodes (WLEDs). Here we report a novel nanocomposite, in which a new type of excited-sate intramolecular proton transfer (ESIPT) molecule, namely 5-(1,2-dithiolan-3-yl)-N-(2-{[4-(3-hydroxy-4-oxo-4H-chromen-2-yl)phenyl](methyl)amino}ethyl)pentanamide (HF-N-LA), is anchored onto the surface of ultrasmall CdSe quantum dots through dithiol functionality. Authentic white light with a CIE coordinate of (0.33, 0.33) could then be generated by confluence of 440 nm emission from CdSe and 570 nm proton-transfer tautomer emission from HF-N-LA. Moreover, linear color tunability could be achieved simply by altering relative amount of the two species, i.e., number of HF-N-LA onto CdSe, in one single nanocomposite, thus opening an innovative route toward applying nanocrystals in the field of WLEDs.

Spectrofluorometric studies on the binding interaction of bioactive imidazole with bovine serum albumin: A DFT based ESIPT process

Bioactive imidazole derivatives were synthesized and characterized by NMR spectra, mass and CHN analysis. An excited state intramolecular proton transfer (ESIPT) process in hydroxy imidazole has been studied using emission spectroscopy. In hydrocarbon solvent, the tautomer emission predominates over the normal emission and in alcoholic solvent like ethanol; a dramatic enhancement of normal emission is observed which was due to increased solvation. DFT calculation on energy, charge distribution of the rotamers in the ground and excited states of the imidazole derivative were performed and discussed. PES calculation indicates that the energy barrier for the interconversion of two rotamers is too high in the excited state than in the ground state. The interaction between bioactive imidazole derivative and bovine serum albumin (BSA) was investigated.

An Intramolecular Charge Transfer Fluorescent Probe: Synthesis, Structure and Selective Fluorescent Sensing of Cu+2

A series of substituted imidazoles have been synthesized in very good yield under solvent free condition by grinding 1,2-diketone, aromatic aldehyde and ammonium acetate in the presence of molecular iodine as the catalyst. The short reaction time, good yield and easy workup make this protocol practically and economically attractive and characterized by NMR spectra, X-ray, mass and CHN analysis. An excited state intramolecular proton transfer (ESIPT) process in hydroxy imidazoles (dpip and dptip) have been studied using emission spectroscopy and it was detected that the two distinct ground state rotamers are responsible for the normal and the tautomer emissions. DFT calculations on energy, dipole moment, charge distribution of the rotamers in the ground and excited states of the imidazole derivatives were performed and discussed. DFT analysis about HOMO, HOMO-1, LUMO and LUMO + 1 were carried out and discussed. PES calculation indicates that the energy barrier for the interconversion of two rotamers is too high in the excited state than the ground state.

Comprehensive Studies on an Overall Proton Transfer Cycle of the ortho-Green Fluorescent Protein Chromophore

Initiated by excited-state intramolecular proton transfer (ESIPT) reaction, an overall reaction cycle of 4-(2-hydroxybenzylidene)-1,2-dimethyl-1H-imidazol-5(4H)-one (o-HBDI), an analogue of the core chromophore of the green fluorescent protein (GFP), has been investigated. In contrast to the native GFP core, 4-(4-hydroxybenzylidene)-1,2-dimethyl-1H-imidazol-5(4H)-one (p-HBDI), which requires hydrogen-bonding relay to accomplish proton transfer in vivo, o-HBDI possesses a seven-membered-ring intramolecular hydrogen bond and thus provides an ideal system for mimicking an intrinsic proton-transfer reaction. Upon excitation, ESIPT takes place in o-HBDI, resulting in a ∼600 nm proton-transfer tautomer emission. The o-HBDI tautomer emission, resolved by fluorescence upconversion, is comprised of an instantaneous rise to a few hundred femtosecond oscillation in the early relaxation stage. Frequency analysis derived from ultrashort pulse gives two low-frequency vibrations at 115 and 236 cm(-1), corresponding to skeletal deformation motions associated with the hydrogen bond. The results further conclude that ESIPT in o-HBDI is essentially triggered by low-frequency motions and may be barrierless along the reaction coordinate. Femtosecond UV/vis transient absorption spectra also provide supplementary evidence for the structural evolution during the reaction. In CH(3)CN, an instant rise of a 530 nm transient is resolved, which then undergoes 7.8 ps decay, accompanied by the growth of a rather long-lived 580 nm transient species. It is thus concluded that following ESIPT the cis-proton transfer isomer undergoes cis-trans-isomerization. The results of viscosity-dependent dynamics are in favor of the one-bond-flip mechanism, which is in contrast to the volume-conserving isomerization behavior for cis-stilbene and p-HBDI. Further confirmation is given by the picosecond-femtosecond transient IR absorption spectra, where several new and long-lived IR bands in the range of 1400-1500 cm(-1) are assigned to the phenyl in-plane breathing motions of the trans-proton transfer tautomer. Monitored by the nanosecond transient absorption, the 580 nm transient undergoes a ∼7.7 μs decay constant, accompanied by the growth of a new ∼500 nm band. The latter is assigned to a deprotonated tautomer species, which then undergoes the ground-state reverse proton recombination to the original o-HBDI in ∼50 μs, achieving an overall, reversible proton transfer cycle. This assignment is unambiguously supported by pump-probe laser induced fluorescence studies. On these standpoints, a comparison of photophysical properties among o-HBDI, p-HBDI, and wild-type GFP is discussed in detail.

Synthesis, Structure, Luminescent and Intramolecular Proton Transfer in Some Imidazole Derivatives

A group of novel 2-aryl imidazole derivatives were synthesized and characterized by NMR spectra, X-ray, mass and CHN analysis. An excited state intramolecular proton transfer (ESIPT) process in hydroxy imidazoles (dmip and dmtip) have been studied using emission spectroscopy and it was detected that the two distinct ground state rotamers of I and II are responsible for the normal and the tautomer emission respectively. In hydrocarbon solvent, the tautomer emission predominates over the normal emission for both dmip and dmtip. This reveal that rotamer II is responsible for the tautomer emission and it is stabler than rotamer I which causes the normal emission. In alcoholic solvent like ethanol, a dramatic enhancement of normal emission is observed which was due to increased solvation, the more polar rotamer I become stabler than rotamer II. In dioxane-water mixtures it is observed that the addition of water inhibits the ESIPT process due to the formation of the intermolecular hydrogen bonding involving water. DFT calculations on energy, dipole moment, charge distribution of the rotamers in the ground and excited states of the imidazole derivatives were performed and discussed. PES calculation indicates that the energy barrier for the interconversion of two rotamers is too high in the excited state than the ground state.

Constrained photophysics of an ESIPT probe within β-cyclodextrin nanocavity and chaotrope-induced perturbation of the binding phenomenon: Implication towards hydrophobic interaction mechanism between urea and the molecular probe

The present work demonstrates the effect of β-cyclodextrin (β-CD) nanocaging on the photophysical properties of Excited-State Intramolecular Proton Transfer (ESIPT) probe 3,5,6-trichlorosalicylic acid (TCSA) through steady-state absorption, emission and time-resolved emission spectroscopy. The remarkable enhancement of tautomer (proton transferred form) emission of TCSA as a result of inclusion complex formation with β-CD has been argued to be principally due to retardation of radiationless decay channels within the encapsulated state. A quantitative assessment of the emission intensity data on Benesi-Hildebrand equation reveals a 1:1 stoichiometry for TCSA:β-CD complex. The steady-state anisotropy, REES, and time-resolved fluorescence decay measurements are consistent with other experimental findings. Additionally, chaotrope (urea)-induced perturbation of the phenomenon of host-guest inclusion complex formation has been elucidated for a series of urea concentration. The present findings have been interpreted on the basis of the hydrophobic interaction mechanism of urea, rather than water 3-D structure rupture. The data unravel that the perturbation of solvation of the β-CD receptor is not important in the presence of urea, while the hydrophobic interaction with free probe molecules could be instrumental behind the observed lowering of TCSA:β-CD binding strength in the presence of urea.

Modulation of Excited-State Intramolecular Proton Transfer Reaction of 1-Hydroxy-2-naphthaldehyde in Different Supramolecular Assemblies

The excited-state intramolecular proton transfer (ESIPT) reaction of 1-hydroxy-2-naphthaldehyde (HN12) has been studied within the interior of the supramolecular assemblies of alpha-, beta-, and gamma-cyclodextrins (CD) and biomimicking environments of ionic (SDS) and non-ionic (TW-20) micelles. Fluorescence measurements are used to investigate the effect of various supramolecular assemblies on the ESIPT reaction by monitoring the large Stokes-shifted tautomer emission of HN12. Enhanced tautomer emission in the microencapsulated state predicts favorable ESIPT reaction in the supramoleuclar assemblies. Benesi-Hildebrand plots have been employed to ascertain that the stoichiometric ratios of the complexes formed between HN12 and CDs are 1:2, 1:1, and 1:1 for alpha-, beta-, and gamma-CD, respectively. The binding constants (K(1)) and free-energy change (DeltaG) for inclusion complexation are also determined from the linearized Benesi-Hildebrand plots. Steady-state fluorescence anisotropy, REES, excitation anisotropy, and fluorescence lifetime measurements are in line with other experimental findings. Differential action of urea on SDS and TW-20-bound probe has also been investigated.

Early events associated with the excited state proton transfer in 2-(2′-pyridyl)benzimidazole

2-(2(')-Pyridyl)benzimidazole (2PBI) undergoes excited state proton transfer (ESPT) in acidic solutions, leading to a tautomer emission at 460 nm. This photoprocess has been studied using ultrafast fluorescence spectroscopic techniques in acidic neat aqueous solutions, in viscous mixtures of glycerol with water, as well as in sucrose solutions. The tautomer is found to be stabilized in the more viscous medium, leading to a greater relative quantum yield as well as lifetime. The long rise time in tautomer emission is not affected by viscosity though. Rather, it appears to have the same value as the long component of the decay of the cationic excited state (C(*)). In addition to the subnanosecond lifetime reported earlier, C(*) is found to exhibit a decay time of 2 ps. This is assigned to its protonation to form the nonfluorescent dication in its excited state (D(*)) considering the ground and excited state pK(a) values reported earlier. An additional rising component of 100 ps is observed in the region of C(*) emission. This is likely to arise from a structural change or charge redistribution in C(*) immediately after its creation and before the phototautomerization.

Substituent and solvent effects on excited state intramolecular proton transfer in novel 2-(2′-hydroxyphenyl)benzothiazole derivatives

A group of novel 2-(2′-hydroxyphenyl)benzothiazole derivatives 1–5 were synthesized with electron-donating or -withdrawing substituent introduced in para position of N atom in benzothiazolyl ring. The excited state intramolecular proton transfer (ESIPT) in 1–5 along with non-substituted 2-(2′-hydroxyphenyl)benzothiazole 6 was studied by means of UV–vis absorption and steady-state fluorescence in solutions. Compounds 1–6 exhibit dual fluorescences including purple normal emission and green tautomer emission. Systematical comparison of the fluorescence of any analogue in a series of solvents ranging from protic ethanol to non-polar hexane demonstrated that polar solvents favor the normal emission while non-polar solvents facilitate ESIPT process and tautomer formation and emission. In either protic or non-polar solvent the tautomer emission intensity of 1–6 decreases consecutively in the order of decreasing electron-donating ability or increasing electron-withdrawing ability of the substituents, on the premise of identical normal emission intensity. This indicates that electron-donating substituents in these derivatives favor ESIPT process and tautomer emission. Competition of intra- and intermolecular hydrogen bonding was studied in dioxane-water binary solvent. It is demonstrated that intermolecular hydrogen bonding with protic solvent impedes ESIPT and tautomer emission. The fluorescent behaviors of 1–6 were interpreted in terms of the population of ground-state rotamers responsible for normal and tautomer emission respectively.

A Comparative Study into Two Dual Fluorescent Mechanisms via Positional Isomers of N-hydroxyarene-1,8-naphthalimides

Three isomers of hydroxy substituted N-aryl-1, 8-naphthalimides based on N-aryl naphthalic anhydride fluorophore have been synthesized. The decrease in fluorescence intensity from ortho to para substitution of hydroxy group on N-aryl reveals that para substituted isomer undergoes ESEC (Excited State with Extended Conjugation) mechanism which is proved by low quantum yield and appearance of dual emission. The ortho isomer, however, has high quantum yield and no tautomer emission, indicating ESIPT (Excited State Intramolecular Proton Transfer) mechanism is not operating. Similarly, all these isomers show strong fluorescence quenching in presence of strong H-bonding solvents like DMSO and pyridine, but there was neither the shift of emission bands nor the appearance of new bands for proton transfer to these solvents. Thus, it also indicates the absence of excited state proton transfer mechanism. Both the ortho isomer, and to a greater degree the meta isomer, showed larger quenching constants (Kapp) with pyridine than DMSO. This trend opposes the hydrogen-bond affinity for these solvents with phenol and points to a 2-point recognition interaction. In addition, a naphthalimide derivative using 2-aminoimidazole was prepared and examined for optimal positioning of a six-membered ring hydrogen bond pattern. No dual fluorescence was observed for this compound either.

Dual Excited-State Intramolecular Proton Transfer Reaction in 3-Hydroxy-2-(pyridin-2-yl)-4H-chromen-4-one

The synthesis, characterization and fundamental of the dual excited-state proton-transfer properties of 3-hydroxy-2-(pyridin-2-yl)-4H-chromen-4-one (1a) are reported. In the electronic ground state, there exist two competitive hydrogen bonding (HB) isomers for 1a. Conformer 1a(O) reveals a five-membered ring HB structure between O-H and carbonyl oxygen, while conformer 1a(N) possesses a six-membered ring HB formation between O-H and pyridyl nitrogen. In a single crystal, the X-ray crystallography unveils an exclusive formation of conformer 1a(N). In solution such as CH(2)Cl(2), 1a(O) and 1a(N) are in equilibrium, and their respective absorption chromophores are significantly different due to different degrees of hydrogen-bond induced pi electron delocalization. Upon excitation, both conformers 1a(O) and 1a(N) undergo excited-state intramolecular proton transfer (ESIPT) reaction. Following ESIPT, 1a(O) gives rise to a tautomer emission maximized at 534 nm in CH(2)Cl(2). Conversely, due to dominant radiationless quenching processes the tautomer emission for 1a(N) cannot be obtained with a steady-state manner but can be resolved from time-resolved fluorescence. Time resolved fluorescence estimates an equilibrium constant of 27 +/- 5 in favor of 1a(N) in CH(2)Cl(2). Ultrafast ESIPT also takes place for the unique 1a(N) form in the crystal. Due to the prohibition of quenching processes in the solid state, bright tautomer emission maximized at 540 nm is resolved for 1a(N) (Phi(f) approximately 0.3). The interplay between two HB conformers with on(1a(O))/off(1a(N)) character in tautomer emission may find future applications such as the recognition of organic Lewis acid/base in organic solvents.

Study on the excited state intramolecular proton transfer of 4′- N, N-diethylamino-3-hydroxyflavone in imidazolium-based room temperature ionic liquids

The excited state intramolecular proton transfer reaction of 4′- N, N-diethylamino-3-hydroxyflavone in imidazolium-based room temperature ionic liquids was investigated by time resolved fluorescent measurements. Dual emission from the normal and the tautomer forms were observed. The normal emission peak position gradually shifts to longer wavelength in the sub ns time region, and the tautomer emission was delayed relative to the normal emission. These results suggest that solvation processes in the earlier time region after excitation play an important role in the proton transfer mechanism.

Effect of β-cyclodextrin nanocavity confinement on the photophysics of robinetin

We have studied the confinement of robinetin, a therapeutically active plant flavonol, in cyclodextrin (CDx) nanocavities, using steady state and time resolved fluorescence spectroscopy. Enhanced tautomer emission (arising from excited state intramolecular proton transfer (ESIPT)) as well as dramatically blue shifted (∼10 nm in β-CDx and ∼33 nm in SHP β-CDx) normal fluorescence observed upon addition of the β-CDxs indicate that robinetin readily enters the doughnut-shaped hydrophobic cavity of β-CDx where the chromone moiety is well shielded from external hydrogen bonding perturbations. Detailed analyses of the fluorescence data (emission profile, anisotropy, decay times) indicate that robinetin forms 1:1 inclusion complexes with both natural and chemically modified β-cyclodextrins (β-CDx and SHP β-CDx) with affinity constant values K = 195 ± 17 M −1 and 1055 ± 48 M −1 respectively, indicating the prospective utility of SHP β-CDx in particular as an effective drug carrier. Unlike β-CDxs, α-CDxs do not form inclusion complexes with robinetin. To further characterize the robinetin/β-CDxs complexes, circular dichroism (CD) spectroscopic studies have been performed, which reveal that incorporation of robinetin molecules in the chiral environment of the β-CDxs strongly affects the electronic transitions of robinetin leading to the occurrence of positive induced circular dichroism (ICD) bands in the near ultra-violet (UV) region. Molecular mechanics calculations show that the inclusion complex with the chromone ring inserted into the β-CDx cavity is most favorable, in agreement with our spectroscopic data.

Excited State Intramolecular Proton Transfer in 2-(2‘-Arylsulfonamidophenyl)benzimidazole Derivatives: Insights into the Origin of Donor Substituent-Induced Emission Energy Shifts

Donor-substituted 2-(2'-arylsulfonamidophenyl)benzimidazoles undergo efficient excited-state intramolecular proton transfer (ESIPT) upon photoexcitation. The tautomer emission energy depends strongly on the substituent attachment position on the fluorophore pi-system. While substitution with a donor group in the para-position relative to the sulfonamide moiety yields an emission energy that is red-shifted relative to the unsubstituted fluorophore, fluorescence of the meta-substituted derivative appears blue-shifted. To elucidate the origin of the surprisingly divergent emission shifts, we performed detailed photophysical and quantum chemical studies with a series of methoxy- and pyrrole-substituted derivatives. The nature and contribution of solvent-solute interactions on the emission properties were analyzed on the basis of solvatochromic shift data using Onsager's reaction field model, Reichardt's empirical solvent polarity scale ET(30), as well as Kamlet-Abboud-Taft's empirical solvent index. The studies revealed that all ESIPT tautomers emit from a moderately polarized excited-state whose dipole moment is not strongly influenced by the donor-attachment position. Furthermore, the negative solvatochromic shift behavior was most pronounced in protic solvents presumably due to specific hydrogen-bonding interactions. The extrapolated gas-phase emission energies correlated qualitatively well with the trends in Stokes shifts, suggesting that solute-solvent interactions do not play a significant role in explaining the divergent emission energy shifts. Detailed quantum chemical calculations not only confirmed the moderately polarized nature of the ESIPT tautomers but also provided a rational for the observed emission shifts based on the differential change in the HOMO and LUMO energies. The results gained from this study should provide guidelines for tuning the emission properties of this class of ESIPT fluorophores with potential applications in analytical chemistry, biochemistry, or materials science.

Dual fluorescence of 1-hydroxy-substituted Nile Red dye in the red and near-infrared spectral range: Excited-state proton transfer along intramolecular hydrogen bond

Photophysical properties of 1-hydroxy-substituted Nile Red dye proved to be entirely different from those of its 2-hydroxy isomer. Strong hydrogen bonding between the 1-HO-moiety and the heterocyclic nitrogen of the molecule made deprotonation with bases very difficult but facilitated photoinduced tautomerization via intramolecular proton transfer. Dual fluorescence was found in all solvents and the relative intensity of the two bands markedly changed with the polarity as well as hydrogen bond donating power of the medium. The quantum yield for both the normal fluorescence and the tautomer emission went through a maximum as a function of the E T(30) solvent polarity parameter with highest values obtained in dichloromethane.