Journal of Applied Spectroscopy, Vol. 72, No.

1, 2005

COLLISIONAL QUENCHING AND DEPOLARIZATION

OF THE FLUORESCENCE OF THE 2,5-DIPHENYLOXAZOLE
AND 2-PHENYLBENZOXAZOLE VAPORS BY OXYGEN

E. V. Dudko, I. I. Kalosha,* and V. A. Tolkachev UDC 535.37+535.338.42

We have measured the constants of collisional quenching and depolarization of the fluorescence of a number
of derivatives of 2,5-diphenyloxazole and 2-phenylbenzoxazole in a gas phase by oxygen. The probabilities of
quenching and orientation randomization of a single collision are determined. It is shown that quenching is
significantly influenced by the electron-donor properties of substituents.

Keywords: oxygen quenching, collisional depolarization of fluorescence, 2,5-diphenyloxazole, 2-phenylbenzoxazole.

Introduction. Oxygen is the key element of energetics in animate nature. The high oxidizing ability of oxy-
gen can manifest itself negatively in naturally occurring physical-chemical transformations, causing degradation and
aging of organic materials. Free radicals (peroxide and hydroxyl ones, superoxide anion radical) formed with participa-
tion of molecular oxygen and singlet oxygen are capable of modifying vital cell components, which can both provoke
diseases and suppress them (photodynamic therapy).
It is known that the primary physical-chemical activation of the neutral molecule of oxygen — formation of
singlet oxygen — can occur when the electronic states of organic molecules are quenched by it. However, despite the
fact that the quenching of excited electronic states of organic molecules by oxygen was discovered and became an ob-
ject of invstigation as early as at the beginning of the past century, its efficiency, just as the accompanying generation
of singlet oxygen, is still unpredictable for lack of knowledge of the quenching mechanism [1]. A burst of practical
interest in the phenomenon was observed in developing dye lasers, where the quenching of the singlet excited state re-
duced the laser effect or even hindered it, while the quenching of the triplet one was, on the contrary, favorable to
lasing. At present, investigations of the interaction of oxygen with excited electronic multiatomic molecules are gaining
great practical urgency also in connection with the constant increase in the concentration of organic pollutants of the
environment and of animate and inanimate nature. The formation of chemically more active excited electronic states of
multiatomic molecules under conditions of natural or artificial light irradiation occurs in nature usually in the presence
of atmospheric oxygen, which in many cases exerts a marked effect on the direction of photochemical transformations
of pollutants. For example, many aromatic hydrocarbons, involved in a chain of photochemical transformations in the
earth’s atmosphere, are transformed into health-hazardous toxic or carcinogenic compounds [2].
In investigating oxygen quenching in solutions, the solvent cell effect smoothes out the differences in the val-
ues of high quenching efficiencies, since the duration of oxygen action is given in this case by the time of its being
in contact with an excited molecule. If the time of interaction necessary for quenching becomes less than the contact
time specified by diffusion, the observed effectiveness of quenching will always be diffusive, irrespective of the real
(collisional) one. In a gas phase, this restriction is absent, or, more precisely, it is replaced by the duration of the col-
lisional contact. However, serious difficulties arise in connection with the determination of gas-kinetic collisional char-
acteristics needed to calculate the frequency of collisions of an excited molecule with a quencher. While the present
experimental methods of determining the lifetime of an excited state provide information with the desired accuracy, the
error for collisional cross section is significantly higher. As for theoretical methods of determining the mentioned char-

*
To whom correspondence should be addressed.

Institute of Molecular and Atomic Physics, National Academy of Sciences of Belarus, 70 F. Skorina Ave.,
Minsk, 220072, Belarus; e-mail: kalosha@imaph.bas-net.by. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72,
No. 1, pp. 43–47, January–February, 2005. Original article submitted July 20, 2004.

0021-9037/05/7201-0043 ©2005 Springer Science+Business Media, Inc. 43

acteristics for complex molecules and their testing under conditions of usual and high temperatures, they are extremely
laborious; therefore approximate data are used that are scarcely amenable to error estimation.
The approach suggested earlier by one of the present authors [3, 4] makes it possible to avoid these difficul-
ties. It is based on combined determination of the characteristics of collisional depolarization and quenching of the
fluorescence of an organic vapor. The approach presupposes a unified gas-kinetic mechanism of collisions resulting in
both quenching of excited states and chaotization of the orientational anisotropy of dipole transition moments with
emission; the chaotization arises upon excitation of a molecular ensemble by a linearly polarized light. The collisional
chaotization of orientation lends itself much more easily to calculation and simulation, because it is based on the uni-
versal mechanism of rotational–translational exchange and enables one to allow for collisions even in the framework
of the dynamics of solid bodies [5–7].
General Relations. Earlier [8], we obtained relations that connect the observed dependences of depolarization
and quenching of the fluorescence of molecules by oxygen with the corresponding molar and gas-kinetic charac-
teristics. Let r0 be the index of the fluorescence anisotropy of the investigated substance under the conditions of a
rarefied vapor, when there are no collisions during the lifetime of an excited stage. On addition of a quenching gas,
the excited state is quenched as a result of collisions with probability q or remains unquenched with probability 1 –
q, but complete chaotization with probability s occurs, i.e., the disturbance of the excitation-induced orientation (the
fluorescence is depolarized). Then the fluorescence anisotropy with index r depends on the concentration [Q] of the
quenching gas as follows:

r0 s (1 − q) τkz [Q] τkc [Q]

=1+ =1+ , (1)
r 1 + qτkz [Q] 1 + τkq [Q]

where τ is the duration of the fluorescence of the substance under study; kz, kc, and kq are the molar constants of the
gas-kinetic frequency of collisions, orientation chaotization (fluorescence depolarization), and quenching, respectively.
Equation (1) makes it possible to draw the obvious inference that at q = 1 the quenching gas does not change the in-
itial polarization of fluorescence.
Using the well-known Stern–Volmer relation for fluorescence quenching, γ0/γ = 1 + τqkz[Q], where γ and γ0
are the quantum yields of fluorescence with a quencher and without it (or of the intensity of fluorescence if the
quencher does not influence the absorption ability and concentration of the luminophor) and expression (1), we get the
relation

−1
(1 − γ ⁄ γ0) ⁄ (r0 ⁄ r − 1) = kq ⁄ kc = (s ⁄ q − s) , (2)

which permits one to find the ratio between the constants of the orientation chaotization and quenching by measuring
only two states: with a quenching gas (r1, γ1) and without it (r0, γ0). For weak quenchers, when q << s, we have kq/kc
= q/s. From relations (1) for an unquenching gas (q = 0) of concentration [M] and a quenching gas of concentration
[Q] and from expression (2) for the connection of kc, kq, q, and s, it follows that

−1 −1 kz,M [M] sM q
((r0 ⁄ r)Q − 1) = ((r0 ⁄ r)M − 1) + , (3)
kz [M] s (1 − q) s (1 − q)

where kz,M and sM are the collision constant and probability of the orientation chaotization of the dipole transition mo-
ment with emission for the unquenching gas. This relation is particularly convenient if the gas-kinetic collision char-
acteristics of quenching and unquenching gases are identical or nearly the same. As such gases, one can use oxygen
and nitrogen that does not quench excited electronic states; the molecules of these gases are very close in their gas-
kinetic collision characteristics [9, 10]. If the assumption that kz,M[M]sM . kz[Q]s is valid, then (3) yields a linear de-
pendence that makes it possible, using the experimentally measured parameters r0/r, to obtain the elementary
probabilities of quenching q and chaotization s for a single collision that are inaccessible for Eqs. (1) and (2):

−1 −1 1 q
((r0 ⁄ r)Q − 1) = ((r0 ⁄ r)M − 1) + . (4)
(1 − q) s (1 − q)

44
 Fig. 1. Dependence of the chaotization coefficient k = kcτ and parameter
⎯⎯m (dashed line) for the vapor of 4,4′-di(tridecafluorohexyl)-p-quaterphenyl
k/√
on the reduced mass m of colliding molecules (dots, experiment; lines, ap-
proximation).

Relations (1) and (2) also enable one to calculate the probability of collisional quenching q, but only for such
quenchers, single collisions with which completely depolarize fluorescence, and it is obvious that s = 1 or under the
condition that the value of s is known (obtained from an experiment or direct theoretical calculation).
The above relations are correct on one important condition that as to the average store of energy the excited
states of molecules correspond to the temperature of the experiment, at which the quenching gas as well as the one
chaotizing the orientation are kept. In this case, exchange by vibrational energy upon collisions does not alter the av-
erage store of the vibrational energy of the excited state. This preserves the intramolecular dynamics, the probabilities
of radiative and (especially) nonradiative transitions, and, correspondingly, the lifetime of an isolated excited state. The
relation will be incorrect if the collisional exchange by vibrational energy leads to changes in the average energy of
excited molecules and, as a consequence, in the lifetime of the excited state, fluorescence intensity, and other charac-
teristics. Therefore, measurements are to be carried out (and were done in the present work) upon excitation by pho-
tons of such frequency ("inversion frequency" [11]) that the average vibrational energy of excited molecules would be
equal to the equilibrium one for the temperature of the medium. On this condition, the integral intensity (quantum
yield) and the law of fluorescence decay do not change upon collisions with the unquenching gas molecules or, after
unquenching collisions, with the molecules of the quencher. If the quantum yield of fluorescence drops with an in-
crease in the store of vibrational energy (temperature) upon excitation in the region of the fluorescence electron tran-
sition, the following rule serves as a criterion of search for the inversion frequency: on addition of an unquenching
gas, a higher frequency of exciting photons produces an increase in the output intensity and fluorescence duration,
whereas a lower frequency produces a decrease. When the quantum yield is increased with temperature (this effect is
extremely rare), we obviously have inverse criteria of search.
Experimental Results and Discussion. The polarization of the fluorescence of the vapor under study was
measured according to the standard orthogonal scheme described in [8] upon excitation by the monochromatized light
of a xenon arc high-pressure lamp with the use of a PEM-90 photoelastic polarization modulator (Hinds Instruments).
The fluorescence was detected by photomultipliers, the signals from which arrived at UPI-2 amplifiers with phase syn-
chronization and then, through analog-to-digital converters of the CAMAC system, were output for computer process-
ing. The absolute error of the polarization degree measured did not exceed 1%.
As noted above, the collisional reorientation is based on a universal kinematic mechanism underlying the
transformation of the translational angular momentum into a reorienting component of the rotational angular momen-
tum in combination with exchange of rotational angular momenta of the partners of collision, i.e., combination of the
mechanisms of translational–rotational and rotational transfers [5, 12]. The probability of the orientation chaotization
upon elastic collision of a multiatomic molecule with oxygen and nitrogen can be assumed to be identical with a small
error. This is illustrated in Fig. 1, which presents the dependence of the coefficients of the orientation chaotization
(fluorescence depolarization) k = kcτ = skzτ of the vapor of 4,4′-di(tridecafluorohexyl)-p-quaterphenyl by inert gases
and by some simple molecules on the effective mass of colliding particles. As the fluorescence duration τ here is the

45
TABLE 1. Probabilities of Quenching of the Excited States (q) and Orientation Chaotization (s) of 2-Phenylbenzoxazoles and
2,5-Diphenyloxazoles by Oxygen

Substance kq ⁄ kc q s
2-Phenylbenzoxazole 0.75 ± 0.10 0.40 ± 0.10 0.56 ± 0.20
2-(4-Dimethylaminophenyl)benzoxazole 0.32 ± 0.10 0.14 ± 0.06 0.50 ± 0.15
2-(4-Methoxyphenyl)benzoxazole 1.30 ± 0.20 0.44 ± 0.10 0.60 ± 0.20
2,5-Diphenyloxazole 1.35 ± 0.15 0.40 ± 0.10 0.70 ± 0.15
2-Phenyl-5-(4,6-dimethyl)phenyloxazole 1.30 ± 0.20 0.40 ± 0.06 0.40 ± 0.10
2-Phenyl-5-(2,5-dimethyl)phenyloxazole 0.90 ± 0.10 0.38 ± 0.06 0.54 ± 0.10
2-Phenyl-5-(3,4-dimethyl)phenyloxazole 1.35 ± 0.10 0.52 ± 0.10 0.58 ± 0.10
2-Phenyl-5-(4-isopropyl)phenyloxazole 1.45 ± 0.15 0.40 ± 0.10 0.34 ± 0.10
2-(4-Cyanophenyl)-5-phenyloxazole 1.20 ± 0.20 0.33 ± 0.10 0.49 ± 0.20
2-(4-Phthalanhydride)-5-phenyloxazole 0.38 ± 0.05 0.18 ± 0.10 0.60 ± 0.20

same, the chaotization coefficients are proportional to the chaotization constants kc. It is seen that the dependence of
the collisional-chaotization constants kc on the reduced mass m of the particles is relatively weak and practically pro-
portional to √⎯⎯m , i.e., the efficiency of reorientation is mainly determined by the reduced angular momentum. More-
over, the total collision cross section of an atom or of a simple biatomic molecule with a complex one is mainly
determined by the cross section of the latter. At the same time, the characteristic features of the gas-kinetic interactions
upon collisions manifest themselves predominantly in the peripheral tangent area of the molecular section, the contri-
bution of which to the total one drops in inverse proportion to the size of the molecule.
To study the dependence of the efficiency of quenching the excited electronic state of complex molecules on
the characteristic features of the structure, we selected a group of substituted 2,5-diphenyloxazoles and 2-phenylben-
zoxazoles. The high quantum yield of fluorescence in combination with the chemical stability favored the widespread
use of this group not only as organic scintillators, but also as working substances of the active media of dye lasers for
UV and adjacent visible ranges of the spectrum, including also the gas phase [13, 14].
Table 1 lists the results obtained in determining the collisional efficiency of quenching (q) and orientation
chaotization (s) of the substances investigated. The dipole fluorescence transition moment of all the substances is di-
rected along the long axis of the molecule, which is confirmed by the correspondence between the observed polariza-
tion degree and that calculated by the method of [15]. This choice was dictated by the necessity of a higher
polarization degree of vapor fluorescence to ensure a better accuracy of measurements. Since in measuring the quench-
ing and chaotization we used two sufficiently independent methods of determining the ratio of the quenching constant
to the chaotization constant [according to relations (4) (nitrogen–oxygen approach) and (2) (measurement of fluores-
cence quenching)], Table 1 presents the averaged results of the determination of kq/kc. The collisional quenching prob-
ability q was found using relation (4). From Table 1 it is seen that the chaotization degrees are very high even for the
smallest (in comparison with the luminophor mass) mass of oxygen and nitrogen molecules. This allows one to assume
the chaotization by more massive quenchers to be practically complete (s = 1) and, correspondingly, to consider it pos-
sible to use relation (2) to obtain the quenching probability q without invoking an auxiliary unquenching gas, as was
done by us when determining the efficiency of perylene self-quenching [8].
The data of Table 1 show that quenching of the excited state of 2,5-diphenyloxazoles and 2-phenylbenzoxa-
zoles by oxygen is their common property. Its maximum efficiency is not 1/3, as is observed for anthracenes [16, 17],
but higher. The efficiency of quenching of 2-(4-dimethylaminophenyl)benzoxazole is almost half that of 2-phenylben-
zoxazole itself. If the assumption that the quenching is most efficient in the collisional contact of oxygen with the re-
gion of localization of a system of conjugate π-electrons is valid, then in this case in 2,5-diphenyloxazoles the effects
of screening the quenching by the volumetric substituents that are not involved in the π-conjugation system must also
manifest themselves. However, this is not observed. For example, 2,5-diphenyloxazole and its dimethyl- and isopropyl-
substituents have almost the same probabilities of quenching of the excited state when they have sufficiently large sub-
stituents that "screen" the π-electron system. It may well be that the reduction of the quenching because of the
screening is compensated by the electron-donor character of the substituents.

46
 There is a clear connection between the electrophilicity of substituents and quenching. For instance, 2,5-
diphenyloxazoles with cyano- and phthalanhydride electron-acceptor substituents are quenched more weakly. On the
contrary, electron-donating methyl- and methoxy-substituents enhance quenching. A similar regularity was found earlier
for oxygen quenching of the vapor of benzene derivatives; a correlation between the increase in the quenching constant
and the fall of the ionization potential of luminophors was established, and an inference was made about the active
role played in quenching by the interaction of triplet oxygen with the singlet excited state of the luminophor S follow-
δ+ δ−
ing the pattern of charge transfer in the contact complex 3(S O2 ) [18, 19]. The generality of this type of interaction
in quenching of the singlet excited state of multiatomic molecules not only by oxygen but also by multiatomic organic
quenchers was also confirmed by the dependence of the quenching effectiveness on the ionization potential [20].
At the present time, the four most probable ways according to which the excited state of complex molecules
by oxygen are quenched have been singled out [1]:
3 − 3 − 3 3 − 3 −
S1 + O2 ( Σg ) → (S1Σg ) → (T1 Σg ) → T1 + O2 ( Σg ) (5)
3 − 3 − 3 1 1
S1 + O2 ( Σg ) → (S1Σg ) → (T1 ∆g) → T1 + O2 ( ∆g) (6)
3 − 3 − 3 3 − 3 −
S1 + O2 ( Σg ) → (S1Σg ) → (T2 Σg ) → T2 + O2 ( Σg ) (7)
3 − 3 − 3 3 − 3 −
S1 + O2 ( Σg ) → (S1Σg ) → (T1 Σg ) → S0 + O2 ( Σg ) (8)
The contribution of the presented processes to the deactivation S1 depends on the relationship between the
levels of the initial and corresponding deactivating complex. In a theoretical analysis of the quenching of fluorescence
of organic molecules-luminophors by oxygen in a stationary contact complex, it was shown that the quenching of the
singlet excited state in channels (5) and (7) is caused solely by the contribution of the charge-transfer mechanism [21,
22]. These mechanisms seem to be responsible, to a certain extent, for the quenching in our case, too.
It is known that a possible way of quenching the excited state of complex molecules by molecular oxygen is
formation of endoperoxide of an excited molecule followed by nonradiative deactivation [23]:

3 3 − 1+ −
(S1 Σg ) ⇔ ( SOO ) ⇔ SO2 (9)

Here, there is transition from the triplet state of the complex to the singlet zwitterion one and then to endoperoxide.
The energies of the bond of oxygen with the complex molecule in the aromatic endoperoxide reach values of order
104 cm–1. The same values for the compound investigated are given by the PM3 method. Therefore, at our tempera-
tures of the vapor (200–300oC) a sufficiently fast decay of endoperoxide must occur.
The possibility of formation of a quasi-stationary collisional complex introduces a new aspect to the physical
meaning of the parameter q. If the lifetime of the excited state in such a complex is less than the complex lifetime
because of the effective quenching, then the parameter q will characterize only the probability of this complex, out in
the presence of purely collisional quenching too — their average effective value.
Conclusions. The results obtained indicate in favor of the assumption on the participation of the mechanism
of charge transfer and of the π-electron system of a molecule in quenching. But in contrast to the condensed phase in
a high-temperature vapor the contact complex of the molecules of a quencher and luminophor is substantially nonsta-
tionary, just as the interactions that specify a quenching mechanism. The relative motion of the nuclear skeletons of
interacting molecules along the collision trajectory scans the intensity and form of interaction of the electron shells
over all the phases of the collisional configuration of nuclei. But the character of these interactions is changed substan-
tially with distance between the components of the complex [21]. That is why the observed final effect of collision is
integral over the entire interaction trajectory. This means that the inferences made for condensed media and even for
a free stationary collisional complex [21] are carefully applicable to impulsive collisional interactions.
The approach used opens up new possibilities of revealing the laws governing oxygen quenching in a pure
collisional form and, first of all, the steric aspects of the mechanism underlying the intermolecular quenching of ex-
cited electronic states of big multiatomic molecules. Its main limitation is, unfortunately, the requirement of the pres-
ence of polarized fluorescence of a vapor.

47
REFERENCES
1. C. Schweitzer and R. Schmidt, Chem. Rev., 103, 1685–1757 (2003).
2. R. Dabestani and I. N. Ivanov, Photochem. Photobiol., 70, 10–34 (1999).
3. V. A. Tolkachev, Izv. Akad. Nauk SSSR, 52, No. 4, 663–667 (1988).
4. V. A. Tolkachev, Zh. Prikl. Spektrosk., 65, 620–634 (1998).
5. S. Clare, A. J. Marks, and A. J. McCaffery, J. Phys. Chem. A, 104, 7181–7188 (2000).
6. A. P. Blokhin, M. F. Gelin, I. I. Kalosha, V. V. Matylitsky, N. P. Erohin, M. V. Barashkov, and V. A. Tol-
kachev, Chem. Phys., 272, 69–76 (2001).
7. A. P. Blokhin and M. F. Gelin, Zh. Prikl. Spektrosk., 70, 478–484 (2003).
8. E. V. Dudko, I. I. Kalosha, and V. A. Tolkachev, Opt. Spektrosk., 74, 1–5 (2004).
9. H. Hippler, J. Troe, and H. J. Wendelken, J. Chem. Phys., 78, 6709–6718 (1983).
10. M. J. Rossi, J. R. Pladziewicz, and J. R. Barker, J. Chem. Phys., 78, 6695–6708 (1983).
11. N. A. Borisevich, Dokl. Akad. Nauk SSSR, 99, 695–698 (1954).
12. A. P. Blokhin and M. F. Gelin, Zh. Prikl. Spektrosk., 70, 196–202 (2003).
..
13. F. P. Schafer, Dye Lasers [Russian translation], Mir, Moscow, (1976), pp. 172–227.
14. N. A. Borisevich and V. A. Tolkachev, Usp. Fiz. Nauk, 138, 545–572 (1982).
15. A. P. Blokhin and V. A. Tolkachev, Opt. Spektrosk., 51, 278–284 (1981).
16. E. J. Bowen, Trans. Faraday Soc., 50, 97–102 (1954).
17. W. R. Ware and P. T. Cunningham, J. Chem. Phys., 43, 3826–3831 (1965).
18. T. Brewer, J. Am. Chem. Soc., 93, 775–776 (1971).
19. R. G. Brown and D. Phillips, J. Chem. Soc., Faraday Trans. 2, 70, 630–636 (1974).
20. T. R. Evans, J. Am. Chem. Soc., 93, 2081–2082 (1971).
21. B. F. Minaev, Zh. Prikl. Spektrosk., 42, 766–772 (1985).
22. B. F. Minaev, V. V. Bryukhanov, G. A. Ketsle, V. Ch. Laurinas, Z. M. Muldakhmetov, Zh. K. Smagulov, and
K. F. Regir, Zh. Prikl. Spektrosk., 50, 291–297 (1989).
23. J-M. Aubry, Ch. Perlot, J. Rigaudy, and R. Schmidt, Acc. Chem. Res., 36, 668–675 (2003).

48