Triplet-Triplet fluorescence of 9,10-dibromanthracene in hexane

The temperature dependence of the triplet-triplet fluorescence (TTF) spectrum of 9,10-dibromanthracene in hexane is studied in the near infrared region between 800 and 1050 nm in the temperature range from 200 to 320 K. The TTF spectrum exhibits two distinct bands at 842 and 949 nm at 293 K. Upon cooling from 293 to 200 K, the intensity of the 842-nm band decreases and that of the 949-nm band increases. The different behavior of the band intensities is explained by the overlap of the emission at 950 nm, which can be related to a photoproduct. The 842-nm band is assigned to the 0-0 T ₂(³ B _1g →T ₁(³ B _2u transition. The quantum yield of TTF at 293 K measured within the 842-nm band is 8.3×10^?7 (±20%)), and for emission in the region from 800 to 1050 nm it is equal to 1.4×10^?6 (after subtraction of the contribution from the S ₁→S ₀ singlet-singlet fluorescence). The effect of the intersystem crossing and internal conversion on the temperature dependence of TTF is discussed.     

Polarity of the Medium and Quenching of Fluorescence of Caratenoids and Phthalimides

The relation for the dependence of the rate of radiationless energy conversion of the S ₁ state k _q on the polarity of the medium, obtained previously by the author, has been used to interpret the known literature data on the lifetime of the S ₁ state of solutions of some caratenoids and phthalimides. It has been shown that in alcohols and water (normal and deuterated ones) the fluorescence quenching of 4-amino-, 4-methylamino-, and 4-dimethylamino-N-methylphthalimides (4AMP, 4MAMP, and 4DMAMP) as well as of peridinine in alcohols is due to H-bond formation. It has been established that a twofold increase in the number of amine atoms of hydrogen on passing from 4MAMP to 4AMP, as well as deuteration of solvents in the case of 4DMAMP, is followed by a decrease in k _q by a factor of 1.6 and 1.75, respectively. The mechanism of quenching in complexes formed with solvent molecules by means of the H-bond is discussed. It has been concluded that the quenching of fluorescence of phthalimides in such complexes is mainly due to the intersystem crossing initiated by the oscillations of the protons or deuterons of the H-bonds.     

Role of the Medium in Radiationless Conversion of the Energy of the Excited S 1 State in Equilibrium Systems with Intramolecular Charge Transfer

Using the Onsager model, the effect of molecular orientation interactions in solutions on the rate constant of radiationless conversion of the energy of the excited S ₁ state has been calculated for equilibrium systems with intramolecular charge transfer. The rate constant of the radiationless conversion of energy S ₁ — X _n is represented as a function of the polarity of the medium f() = ( – 1)/(2 + 1), where is the permittivity of a solvent. The results obtained are compared with the Marcus theory and are also used to explain the well-known literature data on the influence of a solvent on the lifetime of the S ₁ state of some carotenoids.     

Determination of the Dipole Moments of Excited Complexes of Polar Compounds in Proton-Donor Solvents by the Quenching of their Fluorescence

A method of determining the permanent dipole moment of polar compounds in the excited S₁ state by the dependence of the rate of radiationless conversion of the energy of this state on the polarity of the solvent (medium) is proposed. The method was used for determining the dipole moment µ_e of hydrogen-bonded complexes formed by 4-amino-, 4-methylamino-, and 4-dimethylamino-N-methylphthalimides (4AMP, 4MAMP, and 4DMAMP) in proton-donor solvents. It has been established that µ_e = 11.68 D for 4AMP in alcohols, µ_e = 11.84 D for 4MAMP in alcohols, and µ_e = 13.19 D for 4DMAMP in alcohols and water.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 2, pp. 186–191, March–April, 2005.     

Mechanism of alternating copolymerization—I. Kinetic method for the determination of the ratio of constants for the addition of donor-acceptor complexes and free monomers to the propagating centre

A quantitative method for estimation of the extent of donor-acceptor complex participation in the propagating step of radical alternating copolymerization is not yet available. In this paper a kinetic method, based on the dependence of the rate of copolymerization upon monomer feed, is proposed. Four variants of this method, differing in changes of dependence of initiation rate upon monomer feed and in the chosen values of the equilibrium constants, are discussed.     

Band structure of electronic levels and the formation of the fluorescence spectra of polar compounds in polar media

The paper sets out a statistical theory of the effect exerted by interactions of constant dipoles in solutions on the fluorescence spectra of polar compounds. The theory is based on the concept of band structure of the electronic levels of a polar impurity (dissolved) molecule in polar media. Institute of Molecular and Atomic Physics, Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 2, pp. 209–216, March–April, 1997.