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Chemical Physics Letters 517 (2011) 41–45

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Chemical Physics Letters


journal homepage: www.elsevier.com/locate/cplett

Studies of the tautomeric forms of alizarin in the ground state by electronic


spectroscopy combined with quantum chemical calculations
Annaïg Le Person ⇑, Jean-Paul Cornard, Stéphanie Say-Liang-Fat
LASIR, CNRS UMR8516, Université des Sciences et Technologies de Lille, Bât C5, 59 655 Villeneuve d’Ascq Cedex, France

a r t i c l e i n f o a b s t r a c t

Article history: Intramolecular proton transfer of alizarin in the first excited state has been reported previously. In this
Received 15 September 2011 study, we show that this transfer is also present in the ground state. In addition to the absorption of
In final form 7 October 2011 the normal form of alizarin (form A), electronic spectra recorded in methanol exhibit a small absorption
Available online 12 October 2011
band at 560 nm, which is due to the tautomeric form of alizarin (form B). This is confirmed by time-
dependent DFT calculations. At room temperature, we estimate that about 10% of alizarin is under the
form B. The Gibbs free energy of the equilibrium between the two tautomers is evaluated to
1.2 kcal mol1.
Ó 2011 Elsevier B.V. All rights reserved.

1. Introduction transfer which would occur only in the excited state. In the present
work, we have decided to focus our attention on the UV–vis
Over the last 40 years, hydroxyanthraquinones have received absorption and fluorescence spectra of 1,2-HAQ. We will highlight
much attention based on their chromatic properties and are the presence of the tautomeric form B in the ground state and
encountered in many fields such as conservation, restoration, or- study the tautomeric equilibrium and his temperature dependence
ganic dyes [1,2], and medicine [3,4]. In particular, dihydroxyanthr- since nobody, at our knowledge, has investigated this parameter.
aquinones can act as antitumor [5–7] and have antigenotoxic Quantum chemical calculations, performed at the time-dependent
activity [8]. Spectroscopic studies have been already performed density functional theory level will help to explain the results
on hydroxyanthraquinones and emphasized the influence of the achieved by absorption spectroscopy.
position of the substituents on the absorption and fluorescence
spectra [9] and the solvent and pH effects [7,9–11].
Some of these molecules are characterized by intramolecular 2. Experimental
hydrogen bonds relatively stable in the ground and excited states
[12–14] and proton transfer can occur in certain conditions. In par- 2.1. Chemicals
ticular, the intramolecular hydrogen-bonded form of alizarin (1,2-
dihydroxy-9,10-anthraquinone or 1,2-HAQ), which structure is 1,2-HAQ was obtained from Sigma Aldrich and used as received
presented in Figure 1 (form A or 9,10-keto form), have been shown without further purification. Owing to the low solubility of 1,2-
to be much more stable in the ground state whereas intramolecu- HAQ in water, methanol (Chromasolv from Sigma Aldrich, >99.9%
lar proton transfer (ESIPT) from the phenolic OH to the carbonyl purity) was used as the solvent. Anhydrous sodium methoxide
oxygen occurs in the excited state with a great change in molecular CH3ONa was from Acros Organics.
geometry, leading to the tautomeric form B (or 1,10-keto form) [7].
The fluorescence spectra of 1,2-HAQ exhibit dual emission linked
2.2. Spectroscopy
to the coexistence of the two tautomeric forms throughout the ex-
cited lifetime [10] and which has been interpreted by a double
UV–vis spectra were recorded on a CARY 100 (Varian) double-
minimum potential along the proton transfer coordinate. In the
beam spectrophotometer, in the region of 200–700 nm and with
ground state, the lowest minimum is related to the 9,10-keto form,
cells of 1 cm path length. The temperature of the mixture inside
while the minima invert their position in the excited state [13–17].
the cell was controlled by using a thermostatic bath.
Former studies are thus consistent with the existence at the
Emission fluorescence spectra were recorded using a Fluoro-
ground state of the form A of 1,2-HAQ only and with a proton
max-3 (Jobin–Yvon) spectrofluorimeter with slits width varying
from 2 to 8 nm.
⇑ Corresponding author. The spectra decomposition of the data set was performed with
E-mail address: annaig.le-person@univ-lille1.fr (A. Le Person). ORIGIN 7.5 program.

0009-2614/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cplett.2011.10.015
42 A. Le Person et al. / Chemical Physics Letters 517 (2011) 41–45

12 13
8 9 1 2
7 Proton
6 III II I
3 transfer
5 10 4
11 14

Form A (9,10-keto form) Form B (1,10-keto form)

Figure 1. Chemical structures and atomic numbering of the two tautomeric forms of 1,2-HAQ. The O and H atoms numbering is the same as the adjacent C atoms.

2.3. Quantum chemical calculations


(a) Expe
perimental
All calculations were performed at the density functional level
of theory with the hybrid functional B3LYP which employs the
three parameters Becke exchange functional B3 [18] with the x 5
Lee–Yang–Parr nonlocal correlation functional LYP [19], using the
GAUSSIAN (G03) program package [20]. Geometries optimization,

Absorbance
without symmetry constraint, were carried out with the 6-
311+G(d,p) basis set. These functional and basis set have already
been used previously for quantum calculations concerning 1,2- (b) Form A
HAQ [21–25]. Vibrational frequency calculations have been per-
formed to ensure that the optimized structures correspond to en-
ergy minima, with respect to the negative eigenvalues of the
Hessian matrix. In all calculations, solvent effects (methanol) were (c) Form B
taken into account by the SCRF method, via the polarizable contin-
uum model (IEF-PCM). The low lying excited states were treated
within the adiabatic approximation of time-dependent density
functional theory (DFT-RPA). Vertical excitation energies were 200 300 400 500 600
computed for the first 40 singlet excited states, in order to repro- Wavelength (nm)
duce the UV–vis spectra. The calculated absorption energies and
intensities were transformed with the GAUSSSUM program into sim- Figure 2. Experimental, theoretical UV–vis spectra and theoretical positions of
absorption bands calculated for the two forms of 1,2-HAQ, in methanol.
ulated spectra using GAUSSIAN functions assuming a constant band-
width at the half-height of 4000 cm1.

3. Results and discussion Table 1


Experimental and calculated absorption wavelengths (nm) of 1,2-HAQ in methanol.
Only transitions with an oscillator strength >0.05 and molecular orbitals with a
3.1. Presence at the ground state of the two tautomers (UV–vis contribution >15% are reported (H: HOMO and L: LUMO).
absorption spectra)
kexp kcalc f MO contribution
(nm) (nm)
The experimental absorption spectrum of 1,2-HAQ in methanol
(Figure 2) shows three regions: two important absorption bands Form A (9,10- 430 438 0.14 H ? L (84%)
keto) 331 334 0.07 H-3 ? L (90%)
centered on 248 and 430 nm and also a low optical absorption in
301 300 0.09 H ? L + 1 (90%)
the long wavelength range. A spectral decomposition shows the 277 294 0.17 H-4 ? L (82%)
presence of a band centered at 560 nm. The bands in the visible re- 262 256 0.42 H-1 ? L + 1 (72%), H ? L + 2
gion are attributed to p ? p⁄ transitions associated with intramo- (17%)
248 245 0.35 H ? L + 2 (58%)
lecular charge transfers [9]. The maximum at 430 nm is in
207 208 0.28 H-3 ? L + 2 (48%), H-1 ? L + 3
agreement with the 430 nm maximum measured by Sasirekha (20%)
et al. [10] in methanol. But at our knowledge, nobody has detected 204 0.14 H-1 ? L + 2 (58%)
another maximum at a longer wavelength such as 560 nm yet. Form B (1,10- 550 538 0.27 H ? L (71%)
The theoretical wavelengths and oscillator strengths (Table 1) keto) 409 0.05 H-1 ? L (89%)
related to the electronic transitions of the tautomers A and B have 288 0.10 H-5 ? L (85%)
been then calculated by TD-DFT/B3LYP/6-311+G(d,p)/PCM and the 259 0.79 H-1 ? L + 1 (85%)
211 0.08 H-1 ? L + 2 (66%), H ? L + 8
associated theoretical spectra compared to the experimental one
(18%)
(Figure 2). The three experimental regions are well represented 205 0.22 H-1 ? L + 3 (45%), H-3 ? L + 2
by the calculations and can be attributed to the forms A and/or B: (30%)
202 0.09 H-9 ? L (59%)
(i) The UV region is common to both tautomers.
(ii) The transition observed at 430 nm can be attributed to the
transition of the form A calculated at 438 nm and involves (iii) The transition observed at 560 nm can be attributed to the
the HOMO (H) and LUMO (L) orbitals. transition of the form B calculated at 538 nm.
A. Le Person et al. / Chemical Physics Letters 517 (2011) 41–45 43

535 nm (mono-anion) the form A (9,10-keto) is the predominant and more stable one, the
form B (1,10-keto) exists too.
Even though, a test was done to make sure that the band at
higher wavelength is not due to a deprotonated form of 1,2-HAQ.
430 nm (fo
f rm A) The absorption spectra (Figure 3) were measured by adding vari-
ous amounts of a Brönsted base (methanolate) in order to deproto-
r unit)

nate the neutral form of 1,2-HAQ. While the neutral form presents
a maximum at 430 nm, the deprotonated form absorbs at 535 nm
Absorbance (arbitrary

and is well assigned to the mono-anion, as previously showed by


Miliani et al. [7] who measured the spectra in water–dioxane solu-
tions as a function of pH. These authors identified an isobestic
point at 463 nm, exactly the same value as our experiment. We
can thus conclude that the form B (kmax = 560 nm) is not an anionic
form of 1,2-HAQ.
463 nm The comparison of the structural parameters of the two tauto-
(isobestic meric forms in the ground state (Supplementary information)
point)
shows that the ring III is unchanged whereas large structural mod-
ifications are observed for the rings I and II. As expected, an in-
1,2-HAQ without CH 3O- crease of the C1O1 bond length and a decrease of the C9O9 bond
560 nm (Form B)) length are calculated for the form B compared to the form A. In
the same way, among the most marked geometrical changes, the
400 450 500 550 600 650 700
lengths of the C1C2 and C1C13 bonds are calculated larger for
the form B than the form A and the opposite effect is observed
Wavelength (nm) for the C9C13 bond.
Figure 3. Influence of CH3ONa on the spectra of 1,2-HAQ ([1,2-
The frontier orbitals involved in the main calculated transitions
HAQ] = 5  105 mol L1) and absorption bands obtained by spectral decomposition of the two tautomers are depicted in Figure 4. It can be observed
of the 1,2-HAQ without CH3ONa. that these orbitals have approximately the same shape for the
two forms, but they differ by their energies. Consequently, the H-
5 orbital of the form B corresponds to the H-4 of the form A.
Therefore we can conclude that both tautomers are simulta- The electronic distribution of the H orbital is essentially calcu-
neously present in the ground state at room temperature. Although lated over one half of the molecule (rings I and II); this result lar-

Form A Form B

- 0.013 L+ 3
- 0.018 L+ 3

- 0.034 L+ 2 - 0.033 L+ 2

- 0.070 L+ 1 - 0.071 L+ 1

- 0.120 L - 0.127 L

- 0.220 H
- 0.240 H

- 0.265 H-1
- 0.269 H-1

- 0.278 H-3 - 0.281 H-3

- 0.288 H-4
- 0.301 H-5

- 0.376 H-9

Figure 4. Frontier orbitals involved in the main calculated transitions for the two tautomeric forms of 1,2-HAQ (A and B). Energies are expressed in eV.
44 A. Le Person et al. / Chemical Physics Letters 517 (2011) 41–45

gely differs from this reported by Sánchez-de-Armas et al. [23], mostly to the form A decreases while the band at 560 nm related
who have found an orbital distributed over the whole molecule. to the form B grows. This data were used to characterize the tauto-
In contrast, the H-3 orbital is localized on the other part of the mol- meric equilibrium:
ecule (rings II and III). The other frontier orbitals are localized over
A$B
the whole molecule. The calculated transitions mainly have a pp⁄
character. However, one can notice that, except for the H ? L tran- which equilibrium constant is K eq ¼ AeBB =AA
and which Gibbs free en-
 =eA
sition, the assignment of the absorption bands of the two forms to- ergy is Dr G ¼ RT ln K eq , where AA and AB represent the absor-
tally differs. According to the calculated oscillator strength, the bances measured at 430 and 560 nm and assumed to be
H ? L transition is more probable in the form B than in the form attributed to the form A and B, respectively, eA and eB are their
A, indicating that the tautomer B presents a highest absorption respective molar extinction coefficients, R is the ideal gas constant
coefficient than the form A in the long wavelength range. and T is the temperature.
The Gibbs free energy was derived from the slope of the straight
line (Figure 5) ln (AA/AB) versus 1/T, equal to DrG°/R:
3.2. Equilibrium between the tautomers (temperature dependence)
1
Dr G ¼ 1:2  0:3 kcal mol :
The tautomeric equilibrium between the tautomers depends on
the temperature. According to the Boltzmann distribution law, as The uncertainties are quite high because the absorbance at
the temperature grows, the amount of the tautomer A which pre- 560 nm is low (0.1) and the temperature dependence is weak.
sents a larger population at room temperature should decrease The equilibrium constant (Keq), corresponding to the CB/CA ratio,
whereas the tautomer B with a smaller population at room tem- can be estimated to 0.08 at 10 °C and 0.2 at 60 °C.
perature should increase. The electronic spectra were recorded at From the equation of the straight line, the ratio of the molar
different temperatures from 18 to 55 °C (Figure 5) and confirm this extinction coefficients eB (560 nm)/eA (430 nm) was found to be
trend: by increasing the temperature, the band at 430 nm related about 1.5.
The difference of free enthalpy between the two tautomeric
forms computed at the PCM/DFT level of theory is 5.6 kcal mol1.
3 This value is of the same order of magnitude, but at least four times
180 higher than that obtained experimentally. This discrepancy can be
ln (AA / A B) = (618 / T) - 0.3
175 2 partially explained by the fact that the intramolecular proton
R = 0.996
100 x ln (AA / A B)

transfer is assisted by the solvent molecules. Although solvent ef-


170
fects are taken into account in the calculations to describe the sol-
2 vation of the tautomeric form, the influence of the solvent in the H-
165
Absorbance x 10

transfer is totally neglected [26].


18 °C 160

25 °C 155 3.3. Influence of the concentration


30 °C 30 31
4
32
-1
33

1 35 °C 10 / T (K )
Previous studies have shown that the variation of the concen-
40 °C
tration of the solute molecule can modify the intramolecular pro-
45 °C
ton transfer [27]. To investigate this eventual influence on the
50 °C
55 °C studied tautomeric equilibrium, absorption and fluorescence spec-
0 tra were recorded at different concentrations of 1,2-HAQ. From
400 500 600 700 1.0  105 to 1.7  104 mol L1, the absorbance at 430 and
Wavelength (nm) 560 nm linearly varied with the total concentration of 1,2-HAQ
and from 3.0  106 to 5.0  105 mol L1, the same behavior is
Figure 5. UV–vis spectra at different temperatures. Standard free energy of the observed in fluorescence emission (Figure 6). So the studied equi-
equilibrium A M B ([1,2-HAQ] = 5  105 mol L1). librium is not affected by the concentration. The linear regression

A 5x10 6
B λexc = 560 nm
5M5 λexc = 430 nm
4M5
3M5
2M5
Fluorescence intensity

6
1x10
Fluorescence intensity

1M5
9M6
8M6
6
7M6
3x10 6M6
5M6
3M6
5
5x10

0
500 550 600 650 700 750 800
Wavelength (nm) 600 650 700 750
wavelength (nm)

Figure 6. Fluorescence spectra of 1,2-HAQ at two excitation wavelengths (430 and 560 nm, respectively), as a function of the concentration (slits width of 8 nm).
A. Le Person et al. / Chemical Physics Letters 517 (2011) 41–45 45

derived from absorption measurements gives slopes of 4670 and 4. Conclusion


487 L mol1 at 430 nm (form A) and 560 nm (form B), respectively.
From the previously estimated ratio eB/eA, the calculated values of The alizarin excited state intramolecular proton transfer was re-
the molar extinction coefficients are eA 5000 L mol1 cm1 at ported by several authors, in the past. In this Letter, we have
430 nm and eB 7500 L mol1 cm1 at 560 nm. shown, for the first time, that this transfer also takes place, to a les-
These experimental values are in agreement with the calculated ser extent, in the ground state of the molecule. Electronic absorp-
oscillator strengths that predict higher absorption of the form B at tion spectroscopy combined with TD-DFT calculations helped
560 nm than the form A at 430 nm. One can also note that eA is highlight the presence of a tautomeric form at room temperature.
closed to the experimental value determined by Miliani et al. [9] We have shown that the equilibrium between the normal form of
in acetonitrile (4900 L mol1 cm1) or in water-dioxane solutions alizarin (form A) and its tautomer form (form B) depends on the
(4700 L mol1 cm1). temperature and not the concentration of 1,2-HAQ. A value of
1.2 kcal mol1 has been calculated for the free enthalpy of the
3.4. Fluorescence and excited states of both tautomers reaction.

If the two tautomeric forms coexist in the ground state, with a Appendix A. Supplementary data
clear predominance of form A, this is not true in the first excited
singlet state. As shown in Figure 6A, a single band of fluorescence Supplementary data associated with this article can be found, in
is recorded at 638 nm when 1, 2-HAQ is excited at 430 nm, corre- the online version, at doi:10.1016/j.cplett.2011.10.015.
sponding to the maximum absorption of the form A; this has been
verified by a spectral decomposition that indicates the presence of References
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