Journal of Luminescence 81 (1999) 61—70

Photoinduced proton transfer in 3-methyl-6-hydroxy-m-phthalic acid
Ranjan Das , Sivaprasad Mitra , Dipanwita Guha , Samaresh Mukherjee *
Department of Chemistry, J.K. College, Purulia, W. Bengal, India Department of Chemistry, School of Science, Kwamsei Gakuin University, Nishinomiya 662, Japan Department of Physical Chemistry, Indian Association for the Cultivation of Science, Jadavpur, Calcutta 700032, India Received 25 February 1998; received in revised form 13 July 1998; accepted 27 July 1998

Abstract The ground and excited state photophysics of 3-methyl-6-hydroxy-m-phthalic acid (HmPA) has been studied in homogeneous solvents by steady state, nanosecond transient emission spectroscopy and semiemperical AM1 calculations. HmPA shows variations in steady-state spectra depending on the solvent characteristics. A large Stokes-shifted emission in the nonpolar solvent (&9500 cm\,) "325 nm and "470 nm) indicates that on UV excitation the keto form of HmPA undergoes intramolecular proton transfer (ESIPT) leading to tautomerization in the singlet excited state. This particular emission (type-I emission) attributed to the enol tautomer of HmPA, is characterized by a very low emission quantum yield (
&0.08). But in strong hydrogen bonding solvents like ethanol and water another relatively stronger (type-II emission,
&0.3—0.5 depending on the solvent) but small Stokes-shifted fluorescence ( "360 nm and "410—430 nm) is observed. The fluorescence maximum for this particular type of emission depends on the static polarity of the solvent ( varies from 410 nm in ethanol to 430 nm in water). In the ground state, very rapid deprotonation from the carboxylic acid groups occurs in the hydrogen bonding solvent medium resulting in dicarboxylate anion of HmPA. The ground state closed conformer (keto form) of this dicarboxylate anion of HmPA undergoes thermodynamically favourable intramolecular proton transfer in the ground state (GSIPT) leading to the formation of proton transferred form (enol tautomer). All the experimental findings were explained with the theoretical results obtained from CNDO/S-CI calculations. 1999 Elsevier Science B.V. All rights reserved. Keywords: Proton transfer; 3-methyl-6-hydroxy-m-phthalic acid; Solvent effect

1. Introduction Molecules, undergoing excited state intramolecular proton transfer (ESIPT) reaction, are important in connection with promotion of laser action [1], conversion of solar energy into electrical

* Corresponding author. Tel.: #91 33 473 5374; Fax: #91 33 473 2805; e-mail: pcsm@mahendra.iacs.res.in.

energy [2], processes related to the absorption of ultraviolet light by chemical and biochemical systems [3,4] and solvation dynamics [5]. Due to its wide spread applications in science and technology, ESIPT reaction has attracted a number of experimental and theoretical scientists [6]. Although proton transfer reaction of salicylic acid (SA) was known at least four decades ago [7], studies on this system are not very common. This is due to the fact that o-hydroxy carboxylic

0022-2313/99/$ — see front matter 1999 Elsevier Science B.V. All rights reserved. PII: S 0 0 2 2 - 2 3 1 3 ( 9 8 ) 0 0 0 5 0 - 7

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compounds like SA dimerize readily on increasing concentration and get ionized in polar solvents, so that studies of these systems were mainly confined to the derivatives of SA such as methyl salicylate (MS) [8]. But as the experimental techniques have advanced considerably, it has now become possible to use these systems as a probe for ESIPT [9,10]. Again SA and its derivatives are used as charge control additives in dry xerographic toner at low concentrations to control the charging characteristics of toner [11—13]. The technological relevance of ESIPT necessitates a further systematic study on the mechanism of this process. The results of the fluorescence properties of SA and its derivatives have created a long standing debate but the essential features obtained so far can be summarized as follows. Electronic excitation causes the phenolic oxygen to become more acidic which causes ESIPT to occur. Two types of emissions are observed. Type-I emission has very low quantum yield, largely Stokes shifted from the absorption band observed in the hydrocarbon and nonpolar solvents whereas type-II emission observed only in highly polar, protic and aprotic solvents are of relatively larger quantum yield (
). The origin of the two fluorescence bands is not unambiguous. Pant et al. [9] proposed that the strongly Stokes-shifted band is due to the rapid proton transfer in the excited state to give rise to tautomer whereas the normal form emits to give the “blue” band. But Law et al. [10] showed for 3,5-t-butyl salicylic acid (t-BSA) that the carboxylate anion is the only precursor to tautomerization. They also pointed out that a clear view for the mechanism of proton transfer (PT) can be achieved only on the basis of reasonable theoretical calculations. For the last few years, we had been engaged in studying the dynamic aspects of PT reaction in homogeneous and microheterogeneous medium [14—16]. The dynamics of PT in 4-methyl-2,6-diformyl phenol (MFOH) and its derivatives have been discussed in the light of experimental results and theoretical calculations [17,18]. In this present paper we wish to report our findings on 3-methyl-6hydroxy m-phthalic acid (HmPA) with a special emphasis on the elucidation of the mechanism of PT by fluorescence spectroscopy and semiemperi-

cal AM1 and CNDO/S-CI calculations. We have also discussed the photophysical properties of HmPA in comparison to the findings of Law et al. for t-BSA. To clarify the proposed mechanism further, some complimentary studies have been carried out with isophthalic acid (IPHA).

2. Experimental Like 4-methyl-2,6-diformylphenol (MFOH) and 4-methyl-2,6-diacetylphenol (MAOH), 3-methyl-6hydroxy-m-phthalic acid (HmPA) was prepared by the department of inorganic chemistry of this institute in a similar way to that reported earlier [19,20]. Isophthalic acid (IPHA) was received from Merck (Schuchardt) and used as such. The solvents ethanol, cyclohexane, n-hexane and 1,4-dioxane were of spec-grade and used as received. Acetic acid used was of A.R. grade. Triply distilled water was used throughout. Absorption, emission and excitation spectra were recorded on a JASCO 7850 and a Perkin-Elmer MPF 44B spectrophotometer. The transient fluorescence lifetime ( ) was measured with an SP-70 nanosecond spectrometer (Applied Photophysics Ltd., UK) using a pulsed nitrogen lamp based on the time correlated singlephoton-counting technique. Concentration of all the compounds were maintained at 4 to 8;10\ mol dm\. The relative fluoresence quantum yields (
) and all other experimental details were the same as reported earlier [19].

3. Results

3.1. Steady state spectra Fig. 1a shows the electronic absorption spectra of dilute HmPA solution (&10\ mol dm\) in different solvents. A single absorption peak with a maximum at 325 nm is obtained in nonpolar solvents such as cyclohexane, n-hexane and 1,4dioxane whereas in water another shoulder appear at 360 nm region in addition to the 325 nm band. Electronic spectra of HmPA in ethanol show only a single band at 360 nm. The fluorescence emission

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Fig. 1. Absorption (a) and emission (b) spectra of HmPA in 1,4-dioxane (1), water (2) and ethanol (3). [HmPA]"4.3;10\ (M) in each case. Absorption, emission and excitation spectra of IPHA (c): Absorption in ethanol (i); emission (ii) in ethanol (1) and methylcyclohexane (2); excitation in methylcyclohexane (3). [IPHA]"3.8;10\ (M) in each case.

spectra of HmPA (Fig. 1b) in cyclohexane, nhexane and 1,4-dioxane appear at 470 nm with a large Stokes shift (&9500 cm\ from peak to peak) relative to the absorption band (Fig. 1a). The excitation spectra of this band match exactly with the absorption spectra in all the cases. The emission spectra of HmPA (Fig. 1b) in ethanol shows only one peak with a maximum at 410 nm and the peak-to-peak Stokes shift in these cases are rela-

tively small (&3400 cm\). Monitoring the emission at this wavelength, the excitation band appears at 360 nm which is exactly similar to that of the absorption band in ethanol. The mirror image relationship of the fluorescence spectra with the absorption band indicates that the fluorescence emission arises directly from the species absorbed at 360 nm. The 360 nm absorption in ethanol is due to the solvent assisted open conformer of HmPA.

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The emission spectra of water shows a maximum at 430 nm and the corresponding excitation spectra displays a band at 360 nm. We have found no change in spectral properties of HmPA with variation in solution concentration up to &10\ mol dm\. The solutions obey Beer’s law up to this concentration level and it can be inferred that HmPA does not undergo dimerization on increasing the concentration. Even the solid sample of HmPA shows a single large Stokes-shifted emission band at 470 nm. 3.2. Effects of acid and base on the steady state spectral properties Fig. 2 shows the effect of addition of a base like triethyl amine (TEA) on the spectral properties of HmPA in 1,4-dioxane. It is found that with the increasing concentration of TEA the fluorescence

band at 470 nm decreases in intensity, finally disappears and a new band at 410 nm is observed. Addition of base to the solution of HmPA in ethanol causes a large increase in fluorescence intensity and 410 nm band shifted to 430 nm (
"0.33) which is exactly similar to that observed in water, whereas the reverse trend is observed by the addition of acid

Fig. 2. Emission spectra of HmPA in 1,4-dioxane in presence of TEA. [TEA]/mol dm\"0 (0), 2.4;10\ (1), 7.6;10\ (2), 1.3;10\ (3).

Fig. 3. Absorption (a) and emission (b) spectra of HmPA in ethanol, in presence of dilute acetic acid [ACOH]. [ACOH]/mol dm\"0 (0), 1.4;10\ (1), 2.8;10\ (2), 4.2;10\ (3), 5.6;10\ (4), 7.0;10\ (5), 8.4;10\ (6), 9.8;10\ (7).

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in these solutions. The 410 nm band can be assigned as due to the intermolecularly hydrogen bonded complex formed by the interaction with solution medium. The addition of dilute acetic acid in ethanol, causes a decrease in absorbance of 360 nm band with a simultaneous appearance of a second absorption band at 325 nm (Fig. 3a). Also, the steady state fluorescence spectra show some interesting changes in the presence of dilute acid. Increasing the concentration of dilute acetic acid induces a decrease in the fluorescence emission at 410 nm and enhances appearance of a new emission band at 470 nm (Fig. 3b). By the addition of aqueous alkali, in water solution of HmPA, the intensity of 430 nm band increases without any change in position. Accordingly the 430 nm emission band can safely be assigned as due to the anion of HmPA. But the addition of acid has no effect on the spectra of HmPA in hydrocarbon and nonpolar solvents.

3.3. Spectral studies in mixed solvents Addition of water as a cosolvent in pure 1,4dioxane solution of HmPA (keeping the solute concentration fixed always) results in the formation of 360 nm band in the electronic spectra in addition to the 325 nm band (Fig. 4a). The 470 nm emission band in 100% (v/v) 1,4-dioxane undergoes a blue shift to 410 nm in 50% (v/v) dioxane-water mixture. Again, with an increase in the water content of the solvent mixture the emission band at 410 nm shifts to 430 nm (Fig. 4b). 3.4. Decay behaviour of HmPA fluorescence The decay behaviour of HmPA fluorescence obeys single exponential kinetics in all the solvents. In 1,4-dioxane the 470 nm emission decays in a single exponent with a lifetime ( ) value of 3.6 ns. However, the fluorescence at 410 and 430 nm in

Fig. 4. Absorption (a) and emission (b) spectra of HmPA in 1,4-dioxane/water mixture. Vol% of water in (a): 0 (0), 33 (1), 66 (2), 100 (3). Vol% of water in (b): 0 (0), 50 (1), 66 (2), 100 (3).

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ethanol and water decays with lifetime ( ) values of 4.5 and 4.8 ns, respectively. However, the behaviour of HmPA fluorescence in 1 : 1 (v/v) dioxane—water mixture shows biexponential kinetics when monitored at 470 and 410 nm. The relative integrated fluorescence intensities for the 470 and 410 nm components are 35% and 65%, respectively.

4. Discussions The 325 nm absorption band in HmPA is attributed to the intramolecularly hydrogen bonded closed conformer (I, Fig. 5) of HmPA. This is in

analogy with our previous observation made on MFOH in n-hexane and cyclohexane [14]. In ethanol and water, a second absorption band at 360 nm region is observed in addition to the 325 nm band. The measured pH of a solution of HmPA in ethanol and water are 8.3 and 5.0, respectively, which suggest that in these solvents HmPA undergoes rapid intermolecular interaction with solvent medium and results in the formation of hydrogen bonded complex with solvent molecules. This leads us to the fact that the second absorption band or the shoulder at 360 nm region in ethanol and water can be attributed to the intermolecularly hydrogen bonded open conformer. The emission

Fig. 5. Schematic representation of different conformers of HmPA and IPHA: HmPA closed conformer (I), HmPA anion (II), hydrogen bonded complex of HmPA (III) where B is the base added to the solvent medium, IPHA (IV), HmPA tautomer (V) and anion of HmPA tautomer (VI)*.

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spectra in water both in the presence and absence of base appeared at 430 nm indicating the presence of anion of HmPA. In ethanol, on the other hand, a promoter base is necessary for the formation of anion. The 410 nm band in ethanol,or in 1,4-dioxane in presence of TEA, is attributed to hydrogen bonded complex formed due to solute—solvent interaction even in the excited state. Thus complete transfer of proton even in the excited state is possible only in water. On the other hand, the presence of a strong base is necessary for the HmPA anion formation in ethanol. In this connection, our observations are found to be quite different from that of Law et al. for 3,5-ditert-butyl salicylic acid (t-BSA). t-BSA exhibits different absorption bands at 320—324 nm in nonpolar solvents and this absorption band suffers a hypsochromic shift in aprotic solvents as solvent polarity increases. In alcohols, the is found to  correlate primarily to the structure of the solvent molecule rather than the solvent polarity. They found that tends to shift to longer wavelengths  as the steric hindrance around the OH group increases, and they suggest that the blue shifted absorption maxima of t-BSA is due to the formation of solvent—solute complex, presumably through the hydrogen bonding between the OH group in the alcohol and the salicylic acid group in t-BSA. However, we have failed to observe any shift in in going from ethanol to hexanol.  The large Stokes-shifted emission of HmPA in nonpolar solvents at 470 nm is analogous to the spectral features observed for MFOH in nonpolar solvents which suggests that an ultrafast intramolecular proton transfer (ESIPT) across the intramolecular hydrogen bond between phenolic and carboxylic carbonyl groups has taken place [14]. It has been established that if a proton donating hydroxyl group is hydrogen bonded in the ground state, the excited state intramolecular proton transfer (ESIPT) is usually evidenced by a large Stokes-shifted emission in nonpolar solvents, assuming proton transfer occurs during the lifetime of the excited molecules [21]. In the case of HmPA the large Stokes-shifted emission (&9500 cm\) can safely be assigned as due to the ESIPT in nonpolar solvents as is observed in the case of MFOH [14]. The ESIPT has been shown to occur

rapidly as long as the intramolecular hydrogen bond remains unperturbed. In ethanol ESIPT cannot occur due to the stronger interaction with solvent molecules and rupture of intramolecular bond. However, when the proton of phenolic group of HmPA is replaced by a methyl group in methyl 2-methoxy benzoate (MOMB) (III, Fig. 5), a structurally related chromophore of HmPA, a small Stokes-shifted emission from locally excited state is observed around 350 nm. Also, for isophthalic acid (IPHA) (IV, Figs. 5 and 1c) where the phenolic group is absent the absorption and emission bands appear at about 290 and 340 nm, respectively. All these observations clearly indicate that the anomalous large Stokes-shifted emission of HmPA at 470 nm in nonpolar solvents arises due to the enol tautomer (V, Fig. 5) formed due to the ESIPT of the closed conformer (keto form) (I, Fig. 5) of HmPA. To explain the steadystate results we propose the following model (Scheme 1) for the photophysics of HmPA in various solvents. We have observed the second fluorescence band for HmPA at 410—430 nm (type-II) emission which is intense and largely blue shifted relative to the type-I emission (470 nm). Type-II emission seems to originate from photoexcitation of the hydrogen bonded complex (III, Fig. 5) or a form derived from it as described in our model (Scheme 1). This is further substantiated from acid/base effect and mixed solvent experiments. On addition of dilute TEA to a solution of HmPA in pure dioxane, a new band develops at 360 nm in the absorption spectrum, at the expense of 325 nm band. Also, the tautomer band at 470 nm due to ESIPT, decreases in intensity and the band shifts to 410 nm. Following further addition of TEA, the 410 nm band increases in intensity. The addition of dilute acetic acid to a solution of HmPA in ethanol, decreases the absorbance of 360 nm band and another band appears at 325 nm (Fig. 3a). In the emission spectrum, the 410 nm band in ethanol decreases with increasing acetic acid concentration (Fig. 3b) with the appearance of another band at 470 nm. However, in dioxane, addition of dilute acetic acid does not affect the absorption and emission spectrum. All these observations can be explained according to our model.

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Scheme 1. ESIPT and GSIPT in H PA.

On addition of TEA to a HmPA solution of 1,4-dioxane, TEA interacts with CO H groups to  form hydrogen bonded complex of HmPA with a consequent decrease in the 325 nm absorption band. Due to this reason the emission band at 410 nm in ethanol that originated due to hydrogen bonded complex of HmPA or a form derived from it, increases in intensity, followed by a decrease in intensity of the 470 nm band, originating from photoexcitation of neutral closed conformer of HmPA. On addition of acid, the hydrogen bond of HmPA gets ruptured, resulting in the formation of neutral closed conformer of HmPA. Due to this reason, the ground state population of neutral HmPA increases significantly followed by a decrease in population of HmPA complex. As a result, the 410 nm band decreases in intensity and the 470 nm band, attributed to ESIPT phototautomer, develops and increases in intensity. In case of mixed solvent experiments, with increasing vol% of water as a cosolvent in binary solvent mixture of dioxane—water, a second absorption band at 360 nm develops (Fig. 4a). In the emission spectrum the 470 nm band due to enol tautomer shifts to 410 nm at 50% (v/v) water and increases in intensity by addition of water up to 66% (v/v). In 100% water (v/v), the 410 nm band

again shifts to the red at 430 nm. This can be explained by assuming that with increasing vol% of water as a cosolvent, the interaction capability of the solvent media increases with a subsequent formation of dicarboxylate of HmPA. This also results in a blue shift of emission band of tautomer. As the ground state population of HmPA anion increases with increasing vol% of water, the 410 nm band increases in intensity and on further addition of water, this band shifts to 430 nm due to dielectric relaxation and formation of anion. Thus, it appears that in ethanol (in presence of base) and water deprotonation of dicarboxylic acid groups occur in HmPA, resulting in the dicarboxylate anion of HmPA. Our theoretical calculations for CNDO and S—CI show that the dicarboxylate anionic form of HmPA undergoes thermodynamically favourable rapid ground state intramolecular proton transfer (GSIPT), ( Ek ¹) ( E"2.76 kCal/mol, from semiemperical AM1 calculations, R¹+0.59 kCal/mol) to form enol tautomer of ground state dicarboxylate. The ESIPT reaction is characterized by a double well potential energy surface having the reactant in one side and the reaction product (phototautomer) in the other. The barrier height between the stationary points determines the course of ESIPT reaction

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i.e. whether this reaction proceeds via proton tunnelling or as a part of intramolecular vibrational relaxation in a barrierless adiabetic potential. However, the energy barrier for this GSIPT process is found to be +3.1 kCal/mol as revealed by the semiemperical AM1 calculations. This observation suggests that the reaction may proceed via proton tunnelling. Following the photoexcitation of this enol form of ground state, a locally excited emission occurs at 410 nm in ethanol which shifts to 430 nm in water due to dielectric relaxation and formation of anion. In nonpolar, noninteracting solvents ESIPT of the keto form of HmPA occurs resulting in the enol tautomer. The results of the time-resolved emission experiments also support our arguments. In 1,4-dioxane the 470 nm emission decays monoexponentially with a time constant ( ) of 3.6 ns. However, the 410 nm emission in ethanol and 430 nm emission in water decays monoexponentially with time constants ( ) of 4.6—4.8 ns. This observation suggests that the 470, 430 and 410 nm emissions in 1,4dioxane, water and ethanol, respectively, are due to different conformers of HmPA. The mixed solvent experiment for 1 : 1 (v/v) dioxane—water mixture suggests biexponential decay kinetics when monitored at 470 or 410 nm. The relative integrated intensity for the fast decaying component ( "3.5 ns) and slow decaying component ( "5.2 ns) are found to be 34% and 66%, respectively, which suggests coexistence of two excited state species and two ground state species in dioxane—water mixture. However, the more intense type-II emission for HmPA in polar, aprotic and protic solvents is attributed to be originated from photoexcitation of ground state enol tautomer of dicarboxylate anion of HmPA, which results from thermodynamically favourable ground state intramolecular proton transfer (GSIPT) of intramolecularly hydrogen bonded closed conformer of dicarboxylate anion of HmPA. These findings are contrary to observations of Law et al. in respect of t-BSA, where they suggested that the primary photochemical reaction of excited t-BSA is to form deprotonated anion of t-BSA even in nonpolar solvents, and the type-II emission in polar, protic solvents is due to ESIPT of solute—solvent complex.

5. Conclusions The solvent effect, acid—base effect, structural effect experiments and semiemperical AM1 calculations suggest that type-I emission of HmPA occurs due to ESIPT of intramolecularly hydrogen bonded closed conformer or keto form of HmPA. However, the more intense type-II emission of HmPA in polar, aprotic and protic solvents is attributed to originate from photoexcitation of ground state enol tautomer of HmPA, which results from thermodynamically favourable rapid ground state intramolecular proton transfer (GSIPT) of intramolecularly hydrogen bonded closed conformer of HmPA.These findings are contrary to the observations of Law et al. as in case of t-BSA, they suggested the primary photochemical reaction of excited t-BSA is to form deprotonated anion even in nonpolar solvents, and the type-II emission in polar, protic solvents is due to ESIPT of solute—solvent complex. Acknowledgements RD and SM are grateful to CSIR for providing them with Research Fellowships. DG wishes to thank CSIR for providing her with Junior Research Fellowship. References
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