Yu. V. Aksenova

The computational and experimental investigations of photophysical and spectroscopic properties of BF2 dipyrromethene complexes

The electronic excited states of BF2 dipyrromethene (2BrDPM, DPMI, DPMII, PM567 and 4PhDPM) complexes were investigated using the extended multi-configuration quasi-degenerate at the second order of perturbation theory (XMCQDPT2) and the second-order approximate coupled-cluster (CC2) methods. The excitation energies calculated by CC2 are significantly overestimated by 0.42-0.59 eV because of the substantial contributions of double excitation levels to excited states (>10%). However, the calculated XMCQDPT2 excitation energies agree well with experimental ones within the accuracy 0.11-0.20eV. The very low lasing efficiency (7.8-8.4%) of 4PhDPM compound was explained by the T1→T4 and T1→T5 reabsorptions at XMCQDPT2 level of theory. The molecular photonics of pyrromethenes are studied using a combination of the first-principle and semi-empirical calculations. The main mechanism for the deactivation of the energy of the first singlet excited electronic state is the radiative electronic transition for DPMI, DPMII, PM567 and 4PhDPM compounds. Also, the main mechanism for the quenching of fluorescence in considered complexes (except DPMII compound) is the internal conversion. The processes of the internal conversion and intersystem crossing compete with each other in DPMII compound. The measured and calculated fluorescence quantum yields agree well for all considered molecules.

Spectral, luminescent, photochemical, and laser properties of a series of boron fluoride complexes of dipyrrolylmethenes in solutions

We have studied the spectroscopic and lasing characteristics of active media based on two synthesized boron fluoride complexes of alkyl-substituted dipyrrolylmethenes and the photostability of the complexes in comparison with complexes of this kind that were previously studied in the literature under identical excitation conditions. We have determined and analyzed conditions under which new compounds have either merits or drawbacks as compared to the known dye with respect to both lasing efficiency and resource characteristics.

Photonics of zinc(II) and boron(III) chelates with methyl- and phenyl-substituted dipyrromethenes and azadipyrromethenes

A comparative study of spectral, luminescent, and photophysical parameters has been carried out for a series of zinc(II) and boron(III) chelates with dipyrromethene ligands of a similar structure: tetramethyl- and tetraphenylpyrrodimethenes bearing the substituents on the pyrrole rings and tetraphenylazapyromethene. In some cases, the luminescence efficiency of the chelates depends on the excitation wavelength. The replacement of the central atom boron(III) by zinc(II) results in not only a twofold increase in the number of coordinated chromophoric ligands and the absorption coefficient, but also an increase in the contribution of nonradiative processes to excitation energy deactivation and, hence, a decrease in the yield of fluorescence. The efficiency of intersystem crossing is higher in the zinc(II) dipyrromethene complexes than in the corresponding boron-chelated dipyrromethenes (BODIPYs), resulting in the appearance of phosphorescence in frozen solutions. It has been found that the replacement of the meso-spacer in the dipyrromethene ligand by the nitrogen atom not only shifts the absorption and fluorescence band maximums to longer wavelengths, but also decreases the fluorescence efficiency and leads to the appearance of long-lived luminescence even in aza-BODIPY. An analysis of the results has shown that these behavior can be due to involvement of the nπ* (πσ*, σπ*) states localized on the meso-nitrogen in the deactivation of excitation energy.

Spectroscopic and laser characteristics of new efficient luminophores for a wide spectral range based on complexes of dipyrrolylmethene derivatives with difluorine borate

We have studied the spectral-luminescent, lasing, photochemical, and endurance characteristics of a series of new efficiently emitting difluorine borate complexes with dipyrrolylmethenes of different structures. Experimental data have been obtained in polar and nonpolar organic solvents and in solid polymer films involving the participation of silicate structures. We have discussed relations of the structure of investigated compounds and formed solvates with their optical characteristics, and have given guidelines on the use of particular compounds as active media of tunable lasers for determining spectral ranges.

Photophysics of the analogs of pyrromethene PM 567

The spectral and luminescence properties of a number of pyrromethene (PM) dyes have been investigated. The absorption and luminescence spectra of PM molecules in different solvents are measured. The electronic structure and electronic excited states are calculated by the method of intermediate neglect of differential overlap with special spectroscopic parameterization. The rate constants of photophysical processes are estimated, and the fluorescence quantum yields are calculated. The fluorescence quantum yields of PM I and PM II molecules are found to decrease upon their excitation to the second short-wavelength absorption band. This phenomenon is interpreted.

The new laser media of dipyrromethene complexes with boron fluoride

The characteristics of new active media for tuning lasers are presented in liquid and solid state.

Photophysical, photochemical and lasing properties of dipyrrolylmethene complexes in solutions and solid matrices

The spectral-luminescent properties of dipyrrolylmethene derivatives in different solutions and solid silicate matrices doped with these compounds were measured, and their photophysical (γ<inf>fl</inf>, k<inf>rad</inf>, τ<inf>fl</inf>, γ<inf>phos</inf>, τ<inf>phos</inf>), lasing (efficiency, λ<inf>las</inf>), photochemical (ϕ<inf>ph</inf>^355,532), limiting (CL) characteristics were determined. The possibilities of applications are discussed.