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 oxygen 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 participation 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 object 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 reduced 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 values 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 collisional contact. However, serious difficulties arise in connection with the determination of gas-kinetic collisional characteristics 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

one can use oxygen and nitrogen that does not quench excited electronic states. Earlier [8]. because it is based on the universal mechanism of rotational–translational exchange and enables one to allow for collisions even in the framework of the dynamics of solid bodies [5–7]. the chaotization arises upon excitation of a molecular ensemble by a linearly polarized light. using the experimentally measured parameters r0/r. 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 characteristics. the disturbance of the excitation-induced orientation (the fluorescence is depolarized). 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.e. This relation is particularly convenient if the gas-kinetic collision characteristics of quenching and unquenching gases are identical or nearly the same. q. and quenching. but complete chaotization with probability s occurs. kz [M] s (1 − q) s (1 − q) (3) where kz.M [M] sM q + .acteristics for complex molecules and their testing under conditions of usual and high temperatures. (1) and (2): ((r0 ⁄ r)Q − 1) 44 −1 = ((r0 ⁄ r)M − 1) −1 1 (1 − q) + q s (1 − q) . the molecules of these gases are very close in their gaskinetic collision characteristics [9. Then the fluorescence anisotropy with index r depends on the concentration [Q] of the quenching gas as follows: s (1 − q) τkz [Q] τkc [Q] r0 =1+ =1+ . to obtain the elementary probabilities of quenching q and chaotization s for a single collision that are inaccessible for Eqs. and 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. Equation (1) makes it possible to draw the obvious inference that at q = 1 the quenching gas does not change the initial polarization of fluorescence. they are extremely laborious. when there are no collisions during the lifetime of an excited stage. 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). Using the well-known Stern–Volmer relation for fluorescence quenching. i. kc. kq. For weak quenchers. it follows that ((r0 ⁄ r)Q − 1) −1 = ((r0 ⁄ r)M − 1) −1 kz. then (3) yields a linear dependence that makes it possible. therefore approximate data are used that are scarcely amenable to error estimation. γ1) and without it (r0. If the assumption that kz. 10]. γ0). r 1 + qτkz [Q] 1 + τkq [Q] (1) where τ is the duration of the fluorescence of the substance under study. As such gases. kz.M[M]sM . The approach suggested earlier by one of the present authors [3. It is based on combined determination of the characteristics of collisional depolarization and quenching of the fluorescence of an organic vapor.. respectively. The collisional chaotization of orientation lends itself much more easily to calculation and simulation. when q << s. kz[Q]s is valid. (4) . 4] makes it possible to avoid these difficulties. the excited state is quenched as a result of collisions with probability q or remains unquenched with probability 1 – q.M and sM are the collision constant and probability of the orientation chaotization of the dipole transition moment with emission for the unquenching gas. Let r0 be the index of the fluorescence anisotropy of the investigated substance under the conditions of a rarefied vapor. we get the relation (1 − γ ⁄ γ0) ⁄ (r0 ⁄ r − 1) = kq ⁄ kc = (s ⁄ q − s) −1 . we have kq/kc = q/s. and kq are the molar constants of the gas-kinetic frequency of collisions. On addition of a quenching gas. 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. γ0/γ = 1 + τqkz[Q]. General Relations. orientation chaotization (fluorescence depolarization).

This preserves the intramolecular dynamics.. with the molecules of the quencher. If the quantum yield of fluorescence drops with an increase in the store of vibrational energy (temperature) upon excitation in the region of the fluorescence electron transition. through analog-to-digital converters of the CAMAC system.e. The absolute error of the polarization degree measured did not exceed 1%.4′-di(tridecafluorohexyl)-p-quaterphenyl by inert gases and by some simple molecules on the effective mass of colliding particles. measurements are to be carried out (and were done in the present work) upon excitation by photons 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. single collisions with which completely depolarize fluorescence. exchange by vibrational energy upon collisions does not alter the average store of the vibrational energy of the excited state. On this condition. at which the quenching gas as well as the one chaotizing the orientation are kept. 1. fluorescence intensity. experiment. a higher frequency of exciting photons produces an increase in the output intensity and fluorescence duration. This is illustrated in Fig. 1. 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. Relations (1) and (2) also enable one to calculate the probability of collisional quenching q.Fig. 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. the following rule serves as a criterion of search for the inversion frequency: on addition of an unquenching gas. combination of the mechanisms of translational–rotational and rotational transfers [5. Experimental Results and Discussion. whereas a lower frequency produces a decrease. Therefore. correspondingly. the lifetime of an isolated excited state. The fluorescence was detected by photomultipliers. As noted above. 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). 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). after unquenching collisions. When the quantum yield is increased with temperature (this effect is extremely rare). which presents the dependence of the coefficients of the orientation chaotization (fluorescence depolarization) k = kcτ = skzτ of the vapor of 4. as a consequence. approximation). 12]. lines. in the lifetime of the excited state. the integral intensity (quantum yield) and the law of fluorescence decay do not change upon collisions with the unquenching gas molecules or. the signals from which arrived at UPI-2 amplifiers with phase synchronization and then. and other characteristics. i. The relation will be incorrect if the collisional exchange by vibrational energy leads to changes in the average energy of excited molecules and. but only for such quenchers. were output for computer processing. the probabilities of radiative and (especially) nonradiative transitions. As the fluorescence duration τ here is the 45 . and. we obviously have inverse criteria of search. 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 momentum in combination with exchange of rotational angular momenta of the partners of collision. In this case. Dependence of the chaotization coefficient k = kcτ and parameter ⎯m k/√⎯ (dashed line) for the vapor of 4.4′-di(tridecafluorohexyl)-p-quaterphenyl on the reduced mass m of colliding molecules (dots.

40 0. Its maximum efficiency is not 1/3. 46 .10 1.40 0. the characteristic features of the gas-kinetic interactions upon collisions manifest themselves predominantly in the peripheral tangent area of the molecular section. i. Since in measuring the quenching 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 fluorescence quenching)]. The dipole fluorescence transition moment of all the substances is directed along the long axis of the molecule. For example.20 0. but higher. this is not observed.30 ± 0.56 0.20 0. The efficiency of quenching of 2-(4-dimethylaminophenyl)benzoxazole is almost half that of 2-phenylbenzoxazole itself.34 0.60 0. as was done by us when determining the efficiency of perylene self-quenching [8].15 0.10 0. then in this case in 2. 2.10 0.4-dimethyl)phenyloxazole 2-Phenyl-5-(4-isopropyl)phenyloxazole 2-(4-Cyanophenyl)-5-phenyloxazole 2-(4-Phthalanhydride)-5-phenyloxazole kq ⁄ kc 0.5-diphenyloxazoles and 2-phenylbenzoxazoles by oxygen is their common property. Table 1 presents the averaged results of the determination of kq/kc.14 0.5-Diphenyloxazole 2-Phenyl-5-(4.58 0.15 0. we selected a group of substituted 2. correspondingly. Table 1 lists the results obtained in determining the collisional efficiency of quenching (q) and orientation chaotization (s) of the substances investigated. 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.5-diphenyloxazoles and 2-phenylbenzoxazoles. The data of Table 1 show that quenching of the excited state of 2. the contribution of which to the total one drops in inverse proportion to the size of the molecule.40 0.10 0. the efficiency of reorientation is mainly determined by the reduced angular momentum.44 0.06 0. If the assumption that the quenching is most efficient in the collisional contact of oxygen with the region of localization of a system of conjugate π-electrons is valid.38 ± 0.10 0.18 0.33 0.20 0.50 0.20 1. including also the gas phase [13. which is confirmed by the correspondence between the observed polarization degree and that calculated by the method of [15].10 0. the chaotization coefficients are proportional to the chaotization constants kc.70 0. This allows one to assume the chaotization by more massive quenchers to be practically complete (s = 1) and. but also as working substances of the active media of dye lasers for UV and adjacent visible ranges of the spectrum.10 1.20 ± 0.45 ± 0. This choice was dictated by the necessity of a higher polarization degree of vapor fluorescence to ensure a better accuracy of measurements.05 q ± ± ± ± ± ± ± ± ± ± s ± ± ± ± ± ± ± ± ± ± 0. Probabilities of Quenching of the Excited States (q) and Orientation Chaotization (s) of 2-Phenylbenzoxazoles and 2..20 0.75 ± 0.35 ± 0.52 0.TABLE 1.20 0.40 0.38 0.5-dimethyl)phenyloxazole 2-Phenyl-5-(3. The high quantum yield of fluorescence in combination with the chemical stability favored the widespread use of this group not only as organic scintillators.40 0. to consider it possible to use relation (2) to obtain the quenching probability q without invoking an auxiliary unquenching gas.32 ± 0. as is observed for anthracenes [16.10 0.90 ± 0. Moreover.10 0.10 0. To study the dependence of the efficiency of quenching the excited electronic state of complex molecules on the characteristic features of the structure.10 0. The collisional quenching probability q was found using relation (4). At the same time.15 1.15 1.10 0.5-diphenyloxazoles the effects of screening the quenching by the volumetric substituents that are not involved in the π-conjugation system must also manifest themselves.5-diphenyloxazole and its dimethyl.49 0.and isopropylsubstituents have almost the same probabilities of quenching of the excited state when they have sufficiently large substituents that "screen" the π-electron system. 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⎯m portional to √⎯ .10 1.e. However.10 0.54 0.06 0. 17].10 0.30 ± 0. It may well be that the reduction of the quenching because of the screening is compensated by the electron-donor character of the substituents. 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.6-dimethyl)phenyloxazole 2-Phenyl-5-(2.5-Diphenyloxazoles by Oxygen Substance 2-Phenylbenzoxazole 2-(4-Dimethylaminophenyl)benzoxazole 2-(4-Methoxyphenyl)benzoxazole 2.60 0.20 same. 14].06 0.35 ± 0.

there is transition from the triplet state of the complex to the singlet zwitterion one and then to endoperoxide. 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. But the character of these interactions is changed substantially with distance between the components of the complex [21]. too.and methoxy-substituents enhance quenching. just as the interactions that specify a quenching mechanism. electron-donating methyl. These mechanisms seem to be responsible. 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 nonstationary. 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. For instance. The approach used opens up new possibilities of revealing the laws governing oxygen quenching in a pure collisional form and. If the lifetime of the excited state in such a complex is less than the complex lifetime because of the effective quenching. the requirement of the presence of polarized fluorescence of a vapor.5diphenyloxazoles with cyano. 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]. 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. the four most probable ways according to which the excited state of complex molecules by oxygen are quenched have been singled out [1]: S1 + O2 ( Σg ) → (S1Σg ) → (T1 Σg ) → T1 + O2 ( Σg ) S1 + O2 ( Σg ) → (S1Σg ) → (T1 ∆g) → T1 + O2 ( ∆g) S1 + O2 ( Σg ) → (S1Σg ) → (T2 Σg ) → T2 + O2 ( Σg ) S1 + O2 ( Σg ) → (S1Σg ) → (T1 Σg ) → S0 + O2 ( Σg ) 3 − 3 − 3 3 − 3 − 3 − 3 − 3 3 − 1 3 − 1 (5) (6) (7) (8) 3 − 3 − 3 3 − 3 − 3 3 − 3 − The contribution of the presented processes to the deactivation S1 depends on the relationship between the levels of the initial and corresponding deactivating complex. at our temperatures of the vapor (200–300oC) a sufficiently fast decay of endoperoxide must occur.and phthalanhydride electron-acceptor substituents are quenched more weakly. At the present time. 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. unfortunately. The possibility of formation of a quasi-stationary collisional complex introduces a new aspect to the physical meaning of the parameter q. In a theoretical analysis of the quenching of fluorescence of organic molecules-luminophors by oxygen in a stationary contact complex. Its main limitation is. then the parameter q will characterize only the probability of this complex. A similar regularity was found earlier for oxygen quenching of the vapor of benzene derivatives. Conclusions. a correlation between the increase in the quenching constant and the fall of the ionization potential of luminophors was established. out in the presence of purely collisional quenching too — their average effective value. On the contrary. to a certain extent. 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 (S1 Σg ) ⇔ ( SOO ) ⇔ SO2 3 − 1+ − (9) Here. 47 . That is why the observed final effect of collision is integral over the entire interaction trajectory. The same values for the compound investigated are given by the PM3 method. first of all. Therefore. 19]. 22]. The energies of the bond of oxygen with the complex molecule in the aromatic endoperoxide reach values of order 104 cm–1.There is a clear connection between the electrophilicity of substituents and quenching. the steric aspects of the mechanism underlying the intermolecular quenching of excited electronic states of big multiatomic molecules. for the quenching in our case. 2. 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 followδ+ δ− ing the pattern of charge transfer in the contact complex 3(S O2 ) [18.

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