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PII: S1386-1425(18)30780-7
DOI: doi:10.1016/j.saa.2018.08.010
Reference: SAA 16385
Spectrochimica Acta Part A: Molecular and Biomolecular
To appear in:
Spectroscopy
Received date: 5 June 2018
Revised date: 23 July 2018
Accepted
4 August 2018
date:
Please cite this article as: Nutjarin Klinhom, Nikorn Saengsuwan, Suwannee Sriyab,
Panida Prompinit, Supa Hannongbua, Songwut Suramitr , Photophysical properties for
excited-state intramolecular proton transfer (ESIPT) reaction of N-salicylidene-o-
aminophenol: Experimental and DFT based approaches. Saa (2018), doi:10.1016/
j.saa.2018.08.010
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Center for Advanced Studies in Nanotechnology for Chemical, Food and Agricultural Industries, KU
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Institute for Advanced Studies, Kasetsart University, Bangkok 10900, Thailand
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National Nanotechnology Center (NANOTEC), National Science and Technology Development
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Agency, Klong Luang, Pathumthani 12120, Thailand
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Authors to whom correspondence should be addressed: Emails: fsciswsm@ku.ac.th,
based on experimental methods combined with theoretical calculations. The results revealed
that the SA was mainly presented in enol form in acidic solutions while it was predominantly
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existed in keto form in basic solutions. From UV-vis absorption and fluorescence emission
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studies, it showed that the ESIPT could effectively take place in non-polar and aprotic polar
solvents. By using the CAM-B3LYP/6-311G(d,p) level of theory, it was found that the
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intramolecular proton transfer could preferably occur through six-membered ring transition
rather than through five-membered ring transition. The dynamics of the ESIPT reactions of
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enol and keto tautomers were studied using TD-CAM-B3LYP with 6-311G(d,p) basis set.
The potential energy curves for the intramolecular proton transfer in the ground (GSIPT) and
excited state (ESIPT) exhibited that the GSIPT could occur through a low activation barrier,
whereas in the case of ESIPT, the process could arise via low energy barrier.
Highlights
● The quantum chemical calculations based on CAM-B3LYP and TD- CAM-B3LYP with
6-311G(d,p) basis set are an efficient tool for explaining the experimental findings on the
mechanism of enol-keto tautomerization of N-salicylidene-o-aminophenol (SA) dye.
● The tautomerization of the dye depends on pH and polarities of solvents and its
occurrence via ESIPT is much easier than via GSIPT processes.
● The intramolecular proton transfer could preferably occur through six-membered ring
transition rather than through five-membered ring transition.
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Graphical abstract
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1. Introduction
Proton transfer is one of the most important chemical reactions in chemistry and
biology [1]. Various types of proton transfer have been reported in both of ground and
excited states. Excited-State Intramolecular Proton Transfer (ESIPT) is one of the proton
transfer reactions that can be initiated by photo excitation. In recent years, ESIPT has
received increasing attention because of its practical applications in various systems such as
in photostabilizers [2], laser dyes [3], light emitting materials for electroluminescent devices
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[4], molecular switches fluorescence sensors [5], and particularly in biological systems [6-8].
Photo-induced enol-to-keto tautomerization is ESIPT process, which occurs via proton
transfer in the excited state. The shifting of the proton in the excited state consists of proton
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donors (hydroxyl group –OH or amino group –NH2) and proton acceptor groups (carbonyl
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oxygen –C=O or imine nitrogen –N=) in close proximity forming the intramolecular
hydrogen bonding (IMHB) [9]. One of the remarkable characters of the ESIPT process is a
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large Stokes shift in fluorescence. This shift occurs in dual emission without self-reabsorption
which is a desired feature for fluorophores and this enables an effective fluorescence analysis
[10, 11]. In general, the molecules, that the ESIPT process can take place, produce a large
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molecules preferentially are in an enol form at the ground state, which is better stabilized by
the intramolecular hydrogen-bonding than that in a keto form. Upon photo excitation, the
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singlet excited state of the enol form is populated with no geometry relaxation. Then an
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ultrafast ESIPT process, which is much faster than the fluorescence process, occurs and the
excited keto tautomer is produced in a subpicosecond time scale [12-14]. Therefore, the
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fluorescence observed for the ESIPT often occurs due to the keto tautomer. After decaying to
the ground state, the keto form reverts to the original enol form via reverse proton transfer.
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Among the Schiff base molecules, N-salicylidene-o-aminophenol (SA) has received much
interest in widespread for utilization in ion chemosensor, electroluminescence and
photoluminescent devices, magnetic materials, and biological activities [25-30]. The SA dye
possesses two proton donors close to nitrogen atom, which is considered to be
photochromism and thermochromism because of its ability to undergo proton tautomerism
caused by electromagnetic radiation or heat. This property depends on the molecular
planarity, nature of crystal packing, effect of substituent, and nature of the solvent [31]. Due
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to its wide range of applications and an importance of ESIPT in the SA molecule, the
comprehensive studies in both experiments and theoretical calculations are still required.
In this study, photophysical properties for ESIPT reaction of the N-salicylidene-o-
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aminophenol (SA) Schiff base are investigated using experimental methods combined with
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theoretical studies. The effects of pH and polarities of solvents on the ESIPT reaction are
examined. Quantum chemical computations are applied to investigate Intramolecular Proton
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Transfer (IPT) reaction of enol-keto tautomerization mechanism, effect of solvent polarity on
ground state intramolecular proton transfer (GSIPT), electronic transition, and also orbital
diagram.
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2. Experimental section
2.1 Materials and equipment
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All the commercial reagents for the synthesis and solvent were purchased from Sigma
Aldrich and ACI Labscan and used without further purification. Nuclear Magnetic Resonance
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analyses (NMR) were recorded on an INNOVA UNITY VARIAN spectrometer which was
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operated at 400.00 MHz for H-NMR in deuterated chloroform-d (CDCl3) and
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temperature, crystals were formed. After filtration, the crystals were washed with cooled
ethanol and then dried in air. The products were characterized by 1H-NMR and FT-IR
spectroscopies
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2.3 UV-vis absorption and fluorescence emission measurements
UV-vis absorption and fluorescence emission measurements were carried out using
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1×1×3.5 cm3 quartz cells at room temperature. A stock solution (1 mM) of samples was
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diluted to obtain final concentrations of 0.1 mM and 10 µM for UV-vis absorption and
fluorescence emission measurements, respectively. The samples were diluted in various
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solvents with different dielectric constants (𝜀) which are diethyl ether (𝜀=4.33), chloroform
(𝜀=4.81), ethyl acetate (𝜀=6.02), dichloromethane (𝜀=8.93), acetonitrile (𝜀=37.5),
dimethylformamide (𝜀=38.3), dimethyl sulfoxide (𝜀=46.7), ethanol (𝜀=24.5), and methanol
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(𝜀=32.7). The fluorescence spectra were measured at 349 nm, which is an excitation
wavelength of the SA dye. Fluorescence quantum yields of the synthesized compounds were
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determined relatively to quinine sulfate (f= 0.54 in 0.1 M sulfuric acid) [33]. In the study of
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prepared by mixing an aqueous buffer with acetonitrile in the ratio of 6:4 to obtain solvents
with pH ranging from 5 to 12. The phosphate buffer and borate buffer solutions were used.
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intramolecular proton transfer in both ground and excited states [34, 35]. Therefore, the
possible pathway of intramolecular hydrogen bonding mechanism (IMHB) of the dye in both
ground and excited states was investigated using chemical structures of the dye shown in
Figure 1. In this study, enol, ketoA and ketoB are represented the structures in the ground
state, while enol*, ketoA* and ketoB* are represented the structures in the excited state. For
the ground state intramolecular proton transfer (GSIPT), the molecular structures were
carried out based on density functional theory (DFT) calculations. The three parameter hybrid
functional of Becke combined with the correlation functional of Lee, Yang, and Parr
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structure of the S0 state to S1 state using time-dependent density functional theory (TD-DFT)
method and CAM-B3LYP/6-311G(d,p). To calculate emission spectra, geometry
optimization in an excited state was performed for the first excited state (S1) to ground state
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(S0) using the same method [38, 39]. Effect from various solvents including chloroform
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(CHCl3), dichloromethane (DCM) and acetonitrile (ACN), and dimethyl sulfoxide (DMSO)
was also taken into account using the polarizable continuum model (PCM) [39, 40]. The
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potential energy surfaces (PECs) were computed to study the related ESIPT systems, and
were explored by taking the O-H elongation as driving coordinates for the proton transfer
[41]. All quantum chemical calculations were performed using the Gaussian09 computational
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program [42].
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shift of 6000 cm-3 was attributed to normal chromophore. While the large one of 8000 cm-3
was stemmed from the compound formed via ESIPT process, which was keto tautomer in an
excited state (ketoA*) originated from the normal tautomer in an excited state. The presence
of these Strokes shifts confirms the occurrence of ESIPT process of the SA dye in acetonitrile
solution pH=7.
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3.1.2 pH effect for ESIPT
Effect of pH on ESIPT process of SA dye was studied by recording UV-visible
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absorption and fluorescent spectra as shown in Figure 2. Aqueous buffer-acetonitrile (ACN)
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mixtures used in this study were prepared by mixing an aqueous buffer with acetonitrile in
the ratio of 6:4 to obtain solvents with pH ranging from 5 to 12. In ACN solutions pH from 5
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to 7, the UV-visible absorption spectra (Figure 2(a)) exhibited a maximum wavelength at
325 nm. It was found that as increasing in pH from 5 to 7, the absorption intensities of this
band were significantly decreased. At pH 8, low intensity of the band at 325 nm was still
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observed with an occurrence of a new band at 380 nm. As pH increased from 9 to 12, the
absorption intensities of the band at 380 nm were greatly enhanced while the band at 325 nm
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was invisible. The red-shifted absorption of the SA dye from 325 nm to 380 nm as increasing
in pH could be explained in terms of the formation of keto anion in basic solutions [44]. This
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result implied that the SA dye was presented in an enol form in the solutions pH ≤7, whereas
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12 were studied and all emission spectra were shown in Figure 2(b). In solution pH 5, a
strong emission band at 435 nm and a weak emission band at 506 nm were observed in the
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spectrum. The emission intensities of the band at 506 nm were dramatically enhanced as
increasing the pH from 6 to 12, whereas the intensities of the band at 435 nm decreased and
subsequently disappeared at pH >7. From the spectra, the band with lower wavelength at 435
nm could be attributed to the emission of enol tautomer which was stable in solutions pH ≤7,
while the emission band at longer wavelength (506 nm) could conceivably be assigned to
keto tautomer in basic solution (pH >7). An isoemission point for this compound is found at
around 460 nm, which indicates an equilibrium point between the keto and the enol form of
the dye. From the results, it revealed that the dye was presented in both enol and keto forms
at pH ≤7. Although this result was not in agreement with that obtained from the UV-vis
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absorption studies that showed only an enol form existed in this pH range, it suggested that
the ESIPT process of the SA dye could mainly took place in this environment. The change of
UV-vis absorption and fluorescence spectra attributed to the isomerization of SA dye. This
clearly indicates that there are more than two species in equilibrium. The interconversion of
enol and keto forms was outlined in Figure 1. There was the equilibrium between enol and
keto in different pH.
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--- Figure 3 ---
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to compare the difference of benzene ring conformation that affects to an electronic property.
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IKeto is represented as the emission intensity of keto at 506 nm, and IEnol is represented as the
emission intensity of enol at 435 nm. The measurements were carried out in ACN mixtures of
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aqueous buffer with acetonitrile in the ratio of 6:4 using an excitation wavelength at 349 nm.
It showed that IKeto/IEnol ratios increased linearly as rising pH from 5 to 12 with R2 = 0.9559.
This result supported that altering acid-based conditions could lead to the formation of two
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different forms of SA dye, keto and enol, and lead to an occurrence of ESIPT process.
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different polarities and dielectric constants (𝜀) using UV-vis absorption and fluorescence
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emission measurements as shown in Figure 4. The dielectric constants of all solvents as well
as maximum absorption/emission wavelengths of the dye in the solvents were recorded in
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Table 1. The solvents used in this study are diethyl ether (DEE), chloroform (CHCl3), ethyl
acetate (EtOAc), dichloromethane (DCM), dimethylformamide (DMF), dimethyl sulfoxide
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(DMSO), ethanol (EtOH), methanol (MeOH) and acetonitrile (ACN). Figure 4(a) showed
absorption spectra of the dye in the solvents with maximum absorption wavelengths in the
range of 350-360 nm. New band at approximately 450 nm was observed when high polarity
solvents such as aprotic solvents (DMSO, = 46.7) and protic solvents (EtOH, = 24.5 and
MeOH, = 32.7) were used. An appearance of this extra band was caused by interaction
stabilization between hydroxyl group of the solvents and phenol group of the salicylaldimine
enabling high delocalization of the electron cloud on the aromatic system.
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---Figure 4 ---
--Table 1--
The emission spectra of SA dye in all solvents were further studied as shown in
Figure 4(b). It was found that the spectra displayed dual emission wavelengths with a normal
Stokes shift in a range of 404-437 nm and a large Stokes shift in a range of 525-540 nm when
using non-polar solvents (DEE and EtOAc) and aprotic solvents (DCM, ACN, DMF and
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DMSO). The dual emission is caused by an excitation of enol isomer to produce keto isomer
resulting in the presence of ESIPT process. In the case of using protic solvents, the short
wavelength emission bands (<470 nm) disappeared and only emission bands at 525 and 530
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nm were observed in EtOH and MeOH, respectively. The absence of dual emission on the SA
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dye is caused by the presence of intermolecular hydrogen bonding with solvent molecules
leading to stabilization of the solvated keto isomers and prevention of ESIPT process.
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3.2 Quantum chemical calculation
3.2.1 Geometries of the ground states
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In the ground state, enol and keto tautomers could be converted to each other via an
intramolecular proton transfer (IPT) reaction. Enol-keto tautomerization for the SA dye was
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proposed to occur via two pathways based on the fact that nitrogen atom of the azomethine
(proton acceptor) being close to two hydroxyl groups (proton donor) on the phenyl rings. The
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energies of the enol to keto tautomerization on the ground state and its transition states via
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of enol to keto tautomers of the dye through the ground state transition. The calculation
results revealed that enol conformer had lowest geometric energy with optimized
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activation energies of enol, keto and transition state conformations of the dye were calculated
using CAM-B3LYP method with 6-311G(d,p) level of basis set. The calculations were
carried out in solvent phases including chloroform, dichloromethane, acetonitrile, and
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dimethyl sulfoxide. Total energies are considered as the relative energies, which are the
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energy difference between transition state and initial form energies as well as between
transition state and keto form energies in kcal/mol. The results showed that the relative
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energies of transition state with respect to enol form are 8.60, 5.75, 5.59, 5.45, and 4.90
kcal/mol in gas phase, chloroform ( = 4.81), dichloromethane ( = 8.93), acetonitrile ( =
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37.5), and dimethyl sulfoxide ( = 46.7), respectively. It was noticed that the relative energies
tended to decrease as increasing in dielectric constants of the solvents. In the case of relative
energy barriers, which are used to convert keto to enol, the values increased from 0.33, 0.74,
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0.71, 0.78 to 0.88 kcal/mol for gas phase, chloroform, dichloromethane, acetonitrile and
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dimethyl sulfoxide, respectively. It showed that the relative energy barriers increased as
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increasing in dielectric constants of the solvents. This suggested that high stability of keto
could be obtained by using large dielectric constant solvents. From the results, it was evident
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that the solvent polarity and dielectric constant strongly affected the stability as well as
the intramolecular proton transfer of the SA dye tautomers at ground state which could
induce an equilibrium in enol-keto.
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of the dye with oscillator strengths for transition from ground state (S0) to fourth excited state
(S4) and the experimental UV absorption data are listed in Table 2.
--Table 2--
The calculation results showed that the S1 states of SA molecule were mainly derived
from an electronic excitation from the highest occupied molecular orbitals (HOMO) to the
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lowest unoccupied molecular orbitals (LUMO) by 92%. This indicated that the molecule
exhibited in a -* type character. Considering UV-visible spectra in an experiment, there
were two maximum wavelengths (max) at 351 and 268 nm. The first max at 351 nm was
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clearly generated from HOMOLUMO transition and corresponded to the theoretically
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calculated excitation energy at 324 nm. For the max at 351 nm, it was stemmed from H-3→
LUMO (40%) transitions and correlated to the calculated excitation peak at 250 nm. The keto
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forms presented in basic solution produced max at 380 nm, which was attributed to
HOMO→LUMO (97%) transition at 367 nm for the calculated keto structures. All the
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simulated bands showed slightly blue shift of max from the experimental values with
underestimated error of 3-7%, which was in an acceptable range.
To gain more understanding about the mechanism of proton tautomerization inside
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the SA molecule, potential energy curves (PECs) involving the S0 and S1 electronic states
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were calculated as shown in Figure 6. The potential energy profiles were calculated along the
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minimum-energy paths for proton transfer (O-H stretching coordinates from 0.98 to 1.58 Å)
and for ring twisting coordinate. The C1-C2-C3-N dihedral angles of keto tautomers of the
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SA dye were also shown Figure 6. In this studies, the basis of CAM-B3LYP and TD-CAM-
B3LYP methods were used in calculations using optimized geometries of the dye in
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acetonitrile solution. For the calculation of each point of the PECs, bond lengths or dihedral
angles, which were defined as a part of reaction coordinates, were frozen and the other
parameters were allowed to be free for optimization.
The energy profiles along the hydrogen transfer reaction path were displayed
in Figure 6(a). The potential energy curve on the ground state (S0, blue line) clearly showed
that the dye in enol form was more stable than in keto one because it required lesser energy
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than the keto form at 0.98 Å O-H distance. Proton transfers (PT) from O-H group to N atom
in the O-H distances ranging from 0.98 to 1.58 Å were endothermic processes in the ground
state, which required 5.45 kcal mol-1 energy, whereas they exhibited as exothermic reactions
in the S1 excited state. For the excited state (S1, red line), the keto form became more stable
than the enol form because the planar keto-type structure presented above the global
minimum of the excited state (Figure 6(a), last point of the reaction coordinate). The enol*
→ keto* transformation could occur in the excited state through a barrier-less path because of
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no energy barrier in the S1 excited state. This resulted in an emergence of a very large Stokes
shift during an emission. After decaying to the ground state, the photo-tautomer (keto form)
reverted to the original enol form via the barrier for reverse proton transfer of 0.78 kcal/mol.
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This result implied that the presence of GSIPT to convert from enol → keto was more
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difficult than that of the reverse proton transfer process from keto → enol, where it was high
favorable for ESIPT occurrence. The GSIPT was possible to occur when applying thermal
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treatment to the dye to reduce the energy barrier for the process. From the evidences, it
suggested that the GSIPT process was inoperative, while the ESIPT process was feasible in
the SA dye molecule.
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To examine the nature of the PECs with respect to ring twisting, the S0 and S1 energy
profiles along the dihedral angles ( = C1-C2-C3-N) were investigated as shown
in Figure 6(b). PECs of the S0 an S1 states were determined starting from to 180o of
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the PT reaction coordinate. It showed that the twisting around C2-C3 bond was accompanied
by S1 state stabilization of 30 kcal/mol (or 1.30 eV) when compared with the energy
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calculated from out-of-plane distortions. As the C-C torsional angles increased from to
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90o, the S1 PE decreased while the S0 PE increased and they both reached S1→S0 intersection
at = C1-C2-C3-N60°. After the presence of conical intersection, a back proton transfer
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from N-H to O atom could occur and this led to the presence of only enol-form SA molecules
at the end of reaction coordinate. Thus, based on our calculation results, it could be remarked
that the conical intersection between S1/S0 potential energy surfaces played the most
important role in non-radiative deactivation of the SA dye via ultrafast internal conversion of
the excited system to the ground state [14].
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4. Conclusions
In summary, photophysical properties for excited-state intramolecular proton transfer
(ESIPT) reaction of the salicylaldimine (SA) Schiff base have been successfully investigated
using experimental methods combined with theoretical calculations. The results revealed that
the SA dye containing the phenolic proton next to nitrogen of imine group showed pH
dependent behavior under both acidic and basic conditions. The enol form was high stable in
acidic solutions, while the keto form was mainly existed in basic solutions. Emission
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intensity ratio (Iketo/Ienol) studies suggested that the intramolecular proton transfers could
preferably occur through the six-membered ring rather than through the five-membered ring.
It was found that the SA dye showed a single fluorescence emission in polar solvents,
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whereas it exhibited dual emissions with large Stokes shift in non-polar and aprotic solvents
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causing by an excited state intramolecular proton transfer (ESIPT) process. The dynamics of
the ESIPT reactions of enol and keto tautomers were considered based on the potential
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energy curves of the S1 along the proton transfer coordinate. It revealed that the energy
barrier of the enol form was lower than that of the keto form allowing an occurrence of
ESIPT process being more rapidly and easily than that of the keto form. The conical
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intersection between S1/S0 potential energy surfaces of the dye could lead to n-π* character of
the proton transfer product trans-SAketo, which is known as a dark state. This finding is hoped
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that this paper may provide some useful information for ESIPT fluorophore
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Acknowledgements
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Fund (ScRF), and ScAWAKE from Faculty of Science, Kasetsart University. Center of
Nanotechnology Kasetsart University, Kasetsart University Research and Development
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Figure 2. (a) UV-vis absorption and (b) fluorescence emission spectra of SA dye at pH=5-12
in aqueous buffer-acetonitrile (ACN) mixtures.
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Figure 4. (a) UV-vis absorption and (b) fluorescence emission spectra in various types of
solvents.
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Figure 5. (a) Transition state involving hydrogen transfer corresponding to SAenol and SAketo
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tautomerizations via pathway A and B and (b) relative energies of SA on ground state in gas
phase, chloroform (CHCl3), dichloromethane (DCM), acetonitrile (ACN), and dimethyl
sulfoxide (DMSO) solutions calculated by using CAM-B3LYP with a 6-311G(d,p) basis set.
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Figure 6. The calculated potential energy curves of S0 (blue line) and S1 (red line) states as a
function of (a) the hydrogen transfer reaction path and (b) the torsional reaction path
computed by using CAM-B3LYP/6-311G(d,p) method in acetonitrile solution. The energies
of S0 state were calculated under the geometries of the corresponding S1 state.
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Table 1. UV-visible absorption (Abs) and emission (Em ) wavelengths (nm) of SA dye in
different polarities of solvents.
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Ethyl acetate ( = 6.02) 350 420, 536
Polar aprotic solvents
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Dichloromethane ( = 8.93) 357 404, 525
Acetonitrile ( = 37.5) 349 420, 547
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Dimethylformamide ( = 38.3) 354 425, 540
Dimethyl sulfoxide ( = 46.7) 357 437, 534
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Polar protic solvents
Ethanol ( = 24.5) 350 525
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Table 2. Vertical excitation energies (Eex), absorption wavelength (max) and oscillator
strength (f) of enol and keto forms of SA dye calculated using the TD-DFT/CAM-B3LYP/6-
311G(d,p) level of theory in acetonitrile solution.
Vertical excitation
States Expt.
Eex(eV) Eex(nm) fa Transition stateb
cis-enol
S0→S1 3.83 324 0.54 HOMO→LUMO (92%) 351
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S0→S2 4.34 285 0.06 H-1→LUMO (79%)
S0→S3 4.80 258 0.02 H-2→LUMO (34%)
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S0→S4 4.96 250 0.29 H-3→LUMO (40%) 268
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cis-keto
S0→S1 3.24 367 0.40 HOMO→LUMO (97%) 380
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S0→S2 3.97 312 0.01 H-3→LUMO (70%)
S0→S3 4.32 280 0.37 H-1→LUMO (69%)
S0→S4
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trans-keto
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Oscillator strength H = HOMO, L = LUMO, H-1 = next highest occupied molecular orbital and
LUMO
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