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Journal of Luminescence 20 (1979) 283—289

© North-Holland Publishing Company



Walter KLOPFFER and Gerlinde KAUFMANN

Battelle-Institut e. V., D-6000 Frankfurt am Main, Fed. Rep. Germany

Received 14 November 1978

Methylsalicylate (MSA) in vapor state shows two fluorescences originating from two
different ground state species. The short wavelength emission is ascribed to free MSA
molecules with open hydrogen bonds, whereas the blue fluorescence is due to closed
MSA. From a study of the temperature dependence of the short-to-long wavelength fluo- 1.
rescence intensity ratio, the energy required for ring opening is found to be 15 kJ moF

I. Introduction

The fluorescence of methyl salicylate (MSA) in the vapor phase has first been
reported by Marsh in 1924 [1]. He observed at 110°C(17 mbar) two broad emissions
of comparable intensity in the spectral range between 320 and 480 nm. Similar spec-
tra have been observed in solutions of MSA [2—5]in polar solvents, whereas in non-
polar solvents the short wavelength fluorescence (around 360 nm) causes only a weak
shoulder on the main emission band whose maximum is at 450 nm [61.The blue
fluorescence has been interpreted by Weller [61as being due to emission from a
short-lived tautometer (right) produced by proton transfer in the excited electronic
state, whereas the UV emission has been assigned to the excited MSA in its ground

3 OCH3

c~ ®

_ (1)

MSAc *

From fluorescence quenching experiments and measurements of the temperature

284 W. Klopffer, G. Kaufmann I Methyl salicylate in the vapor phase

state configuration (left): dependence of the two emissions Weller [2,6] concluded
that the two excited state tautomers are in equilibrium, the potential energy of the
proton in the H-bond being nearly equal in its two positions. In polar solvents, how-
ever, at least two different ground-state species have been shown to be present [3—5]:




This was concluded from the dependence of fluorescence on excitation wavelength.

The 450 nm fluorescence is emitted after excitation of the closed ring from MSAc
and excited state proton transfer, while the 350 nm fluorescence is due to solvated
MSAs molecules [3—51. A weak dependence of the UV emission of MSA in cyclo-
hexane [5] and methyl cyclohexane [7] on the exciting wavelength seems to indicate
a similar 2-species mechanism even in non-polar solvents; this, however, requires more
detailed research using highly purified solvents in order to prevent spurious effects of
hydrogen-bond-breaking impurities, e.g. traces of water. In this paper we wish to
describe some experimental results obtained in following up the early work of Marsh
[1] in the gas phase. It will be shown that the two types of emission observed by
Marsh are due to two species, one of which causes the short wavelength fluorescence
and is formed in low concentration by a thermally activated process. Excited state
proton transfer, which has been studied so far only in the condensed phase [8], is
indicated by the broad 450 nm band.

2. Experimental

2.1. Absorption spectra

The vapor phase absorption spectra at room temperature were obtained with a
Beckman ACTA-M 6 by equilibrating a few drops of MSA in a 10cm quartz cuvette.
UV spectra at temperatures up to 160°Cwere obtained by using 1 cm quartz cells
.and a variable-temperature accessory (Beckman).
W. Kidpffer, G. Kaufmann I Methyl sailcylate in the vapor phase 285

2.2. Fluorescence spectra

The fluorescence spectra were recorded with a Hitachi—Perkin—Elmer MPF 2A

fitted with a temperature cell variable within the range from 20 to 90°C.The MSA
vapor was introduced into dry 1 cm quartz cells by equilibrating in an atmosphere
consisting of dry nitrogen saturated with MSA. The cells were closed with teflon
stoppers in the glove box where equilibrating took place, and then transferred into
the spectrometer.

2.3. Materials

Most of the experiments were carried out with an MSA sample whose purification
has been described previously [3]. In addition, partly deuterated MSA was prepared
by reacting MSA with D2 0. The degree of deuteration was found by NMR and IR to
be about 60%. The nitrogen gas used had a purity of 99.996%.

3. Results

3.1. Vapor-phase UV-absorption spectra

Fig. 1 shows a room temperature absorption spectrum of MSA which exhibits two
distinctly different bands:
a broad absorption band with a maximum at 303 nm, probably an intramolecular
charge transfer band [8], and
a structured absorption with a maximum at 234 nm similar to the usual absorption
of aromatic hydrocarbons. The molar decadic absorption coefficients can be calcu-
lated using the published vapor pressure curve (log10 p = —2765.9/K + 8.SOO;p given
in Torr) [9]; the partial pressure at 25°C(0.166 Torr = 0.221
1. Thembar) corresponds,
absorption coeffi-
e.g., toe(303)
cients a concentration
= 3100 andof e(234)
9.75 1Xmol1
106 cm’
mo11 are somewhat smaller than
those reported for MSA in aliphatic hydrocarbons [8]. When studying the UV-
absorption spectra as a function of temperature between 50 and 150°C,no signifi-
cant changes were found in the
— position of absorption maxima,
— bandwidth and
— relative absorbance at 234 and 303 nm.
The partially deuterated MSA shows an identical absorption spectrum.

3.2. Fluorescence spectra

Typical fluorescence spectra of MSA vapor in dry nitrogen at 50°Care shown in

fig. 2 for two exciting light wavelengths:
286 W. Kidpffer, G. Kaufmann I Methyl salicylate in the vapor phase

i.e — _____________________________________________

- t~24.1°C


200 250 300 350

Fig. 1. Vapor phase UV absorption spectrum of MSA, saturated d = 10 cm, partial pressure p =

0.215 mbar (calculated [9]), corresponding to 9.17 X 10~ M.

— curve (a), excitation at 320 nm, shows the characteristic broad 450 nm fluores-
cence, which is known from solution spectroscopy;
— curve (b), excitation at 304 nm, shows in addition a second emission, at even
shorter wavelength (about 330—340 nm) than that of the fluorescence of the
solvated broken ring form (MSAs) in polar solvents (maximum near 355 nm) [3].
Qualitatively, the spectrum excited at the short wavelength is similar to that reported
by Marsh [1] and also very similar to spectra obtained from the partially deuterated
MSA under identical conditions. In some cases, a shoulder near 355 nm has been ob-
served and tentatively ascribed to MSAs molecules associated with water-molecules;
experiments using water-saturated nitrogen gas, however, failed to produce this band.
Increasing the temperature was found to cause a strong increase in the short wave-
length fluorescence intensity, whereas the blue fluorescence turned out to be nearly
temperature independent. Fig. 3 shows several of the spectra obtained at different
temperatures, using 290 nm excitation. Lowering the temperature after heating
again yields the spectrum characteristic of the lower temperature; only after an
extended irradiation time do new peaks appear which can probably be attributed to

~ 304nm
• Exc.

300 350 400 450 500 nm 550

Fig. 2. Vapor phase fluorescence spectra (uncorrected) of MSA at 50°C,equilibrium pressure
under N2, excitation wavelengths and spectral slit width indicated. The experimental conditions
are identical for both spectra.


I \ 1(333)
- 1(450)

~ I
I/ \\\~\
\ \~ 2.5 3.0 1000/1 3.5 K

300 350 400 450 500 nm

Fig. 3. Vapor phase fluorescence of MSA, under N
2, as a function of temperature (indicated in
°C).Insert: semilogarithmic plot of the intensity ratio of short-to-long wavelength emission vs.
reciprocal temperature.
288 II’. Kidpffer, G. Kaufmann I Methyl saucy/ate in the vapor phase

irreversible photochemical reactions. The increase in total fluorescence intensity at

the relatively low temperatures shows that some supersaturation, probably adsorp-
tion at the walls of the cell, must have occurred during the saturation process in the
glove box. The insert in fig. 3 shows that the intensity ratio of short-to-long wave-
length fluorescence decreases exponentially with I IT.

4. Discussion

MSA in the vapor phase clearly shows two different fluorescences whose relative
intensity depends on the excitation wavelength and the temperature:
a blue fluorescence (emission maximum 450 nm, excitation maximum 319 nm) and
a UV fluorescence (emission maximum 335 nm, excitation maximum 303 nm).
The existence of distinctively different excitation maxima for the two emissions
points to two ground-state species as the origin of the two fluorescence bands rather
than to an excited state equilibrium. The species showing blue fluorescence corre-
sponds to the main fluorescent form in non-polar solvents, the large Stoke’s shift
being due to intramolecular proton transfer in the excited state [6]. The rate of
excited-state intramolecular proton transfer has recently been measured directly by
Shizuka [10] for N-heterocycles containing intramolecular hydrogen bonds. This
rate has been found to be of the order of 1010 s~1proton transfer is therefore sup-
posed to effectively compete with the other deactivation processes of MSAc* in
its ground-state configuration. This species has a closed hydrogen-bonded ring both
in the ground state and in the first excited singlet state. The UV fluorescent species
emitting at shorter wavelengths than observed for the solvated form MSA5 most
probably is free MSA with an open hydrogen bond (MSAo):

3 OCH3

The equilibrium constant for this reaction occurring in the electronic ground state is
given by
K = [MSAo]/[MSAc]. (4)
From the independence of the UV absorption spectrum on temperature on the one
W. K/dpffer, G. Kaufmann I Methyl ga/icy/ate in the vapor phase 289

hand and the clearly different excitation spectra for the two emissions on the other,
it may be concluded that only a small fraction of the photons is absorbed by the UV
emitting from (MSAo) even at short wavelengths (<310 nm). Since, furthermore, the
absorbance (d = 1 cm) is very small, the intensity ratio of short-to-long wavelength
fluorescence is proportional to K, provided that the quantum efficiencies of the two
emissions do not strongly depend on temperature. The slope of the semilogarithmic
plot in fig. 3 then gives the enthalpy of the reaction (3). This quantity is found to be
MI = + 15 kJ mol~1and corresponds to the energy needed for breaking the intra-
molecular hydrogen bond. It is substantially smaller than the value estimated for the
strength of the hydrogen bond in MSA on the basis of spectroscopic data (28 kJ
mol’) [11] and in much better agreement with the results of a measurement using
ultrasonic relaxation in liquid MSA (10.5 kJ mol~)[12]. -

Since the entropy change ~S of reaction (3) is most probably very small, we can
estimate the equilibrium constant K according to

~ (5)

and find that the equilibrium concentration of MSAo is of the order of a few tenths
of a percent (K = 0.0025 at 25°C);this explains the observed independence of UV
absorbance from temperature. The fact that the short wavelength fluorescence, which
is due to MSA0*, nevertheless is so strong, points to a high quantum efficiency of
MSAo compared with that of MSAc. Fluorescence spectroscopy therefore provides a
very sensitive tool in probing this seemingly very simple chemical reaction.


This work has been performed as part of the Battelle Corporate Technical Devel-
opment Program.


[1] J.K. Marsh, J. Chem. Soc. 125 (1924) 418.

[2] I-I. Beens, K.l-I. Grellmann, M. Gurr and A. Weller, Disc. Faraday Soc. 39 (1965) 183.
[3] W. Klbpffer and C. Naundorf, J. Luminescence 8 (1974) 457.
141 E.M. Kosower and I-I. Dodiuk, J. Luminescence 11(1975) 249.
[5] K. Sandros, Acta Chem. Scand. A30 (1976) 761.
[61 A. Weller, Z. Elektrochem. 60 (1956) 1144.
[7] W. Klöpffcr and G. Kaufmann, unpublished results.
[8] W. Klbpffer, in: Advances in photochemistry, eds. J.N. Pitts, Jr., G.S. Hammond and K.
Gollnick, vol. 10 (Interscience, New York, 1977) p. 311.
[9] Handbook of Chemistry and Physics, 54th ed. (CRC Press, 1973/74).
[10] H. Shizuka, K. Matsui, Y. Hirata and 1. Tanaka, J. Phys. Chem. 81(1977) 2243.
[11] B.A. Zadorozhnyi and I.K. Ishchenko, Opt. Spectry.(Engl. Transl.) 19(1965)306.
[12] T. Yasunaga, N. Tatsumoto, H. Inoue and M. Miura, J. Phys. Chem. 73 (1969) 477.