Fluorescence quenching of vaporous polycyclic aromatic hydrocarbons by oxygen

National audienceThe fluorescence quenching by oxygen of vapors of nine polycyclic aromatic hydrocarbons with strongly different oxidation potentials 0.44 eV < E ox < 1.61 eV (anthracene, 9-methylanthracene, 2-aminoanthracene, 9,10-dibromanthracene, pyrene, chrysene, phenanthrene, fluoranthene, and carbazole) is studied. From the dependences of the fluorescence decay rates and intensities on the oxygen pressure P O2, the quenching rate constants k S O2 for the excited singlet states S 1 and the fraction f S O2 of the S 1 states quenched by oxygen are estimated. At P O2 = 5 Torr, the k S O2 constants vary from 1.2 × 107 to 3.0 × 105 s−1 Torr−1, while the fraction of the quenched excited singlet states changes from 0.1 (fluoranthene) to 0.7 (chrysene) and 0.8 (pyrene). The dependences of k S O2 on the photophysical and electron-donor characteristics of the fluorescing compounds are analyzed. It is shown that, in the gas phase of anthracene and its derivatives, the magnitudes of k S O2 are limited by the rate constants of gas-kinetic collisions k gk and do not depend on the electron-donor characteristics of fluorophores, while the fraction of quenched states f S O2 changes with the oxidation potential. For compounds with k S O2 < k gk, both the rate constants k S O2 and the fraction of quenched states f S O2 depend on the E ox of sensitizers, which demonstrates an important role played by the charge-transfer interactions in quenching of the S 1 states. The dependence of the rate constants k S O2 on the free energy of electron transfer ΔG et is considered

Luminescent Probe for Highly Energetic Collisions in Mixtures of Complex Molecules with Acceptors of Vibrational and Triplet Energy

Pressure dependences of intensities and decay rates of time-resolved luminescence of acetophenone, benzophenone, anthraquinone were used to obtain the efficiencies of vibrational and triplet-triplet energy transfer. It was shown that vibrational relaxation of the chosen molecules can be interpreted in terms of two consecutive processes: rapid collisional relaxation of molecules from initially prepared states to a vibrational distribution at T$\text{}_{vib}$ by vibration-vibration process and relaxation of this vibrational distribution to the thermal one (vibration-translation process). At relatively small internal energy < 10000 cm$\text{}^{-1}$, the collisional efficiencies of the vibration-vibration process in mixtures with polyatomic bath gases had values typical of processes with a supercollision contribution. Molecules relaxed from the upper vibrational level to the vibrational distribution after several collisions (2-3). The average energies transferred per collision are well correlated with predictions of the simple ergodic theory of collisional energy transfer. The majority of the collisions took part only in vibration-translation energy transfer of relatively small energies. The efficiencies of triplet-triplet energy transfer were analyzed for acetophenone, benzophenone and anthraquinone as donors and biacetyl-acceptor in a gas phase when energy of about 20000 cm$\text{}^{-1}$ was transferred. It permitted us to elucidate the common features of highly energetic collisions. It was shown that the efficiencies are much lower than the gas kinetic ones and depended on the vibrational energy and temperature. It was discussed how to enhance triplet-triplet efficiencies due to vibrational excitation of a donor molecule