Absorption and Fluorescent Properties of Pyrylium Compounds: II. Spectra and Cross Sections for Absorption from the Ground and Excited States of the Structurally Rearranged Form

摘要

The nonstationary absorption of solutions of 2,4,6-substituted pyrylium salt is studied by the pumpprobe method. The solutions in methylene chloride are studied upon picosecond pumping and probing with different time delays. The solutions in methyl ethyl ketone are studied upon pumping and synchronous probing by nanosecond pulses. It is shown that excitation of the initially nonplanar molecule causes its structural rearrangement. As a result, substituent 2 enters into the pyrylium ring plane and two nonstationary conformers are formed that differ in the position of substituent 6. The motion upon structural rearrangement has a small amplitude, and localization of molecular orbitals changes only slightly. The temperature dependence of the nonstationary absorption is studied in the range from 293 to 223 K. The spectra and cross sections are measured for transitions from the S_0 and S_1 states. In addition, the activation energies and kinetic parameters of the rearrangement in the ground and excited states are determined. Experimental data are compared with theoretical calculations of the transitions from the S_1 state. It is shown that a partial flattening of conformer molecules results in the long-wavelength shift of the bands and an increase in the cross sections for transitions localized on a flat part of the molecule and does not change parameters of the band localized on the molecular part that did not change upon the rearrangement but remained nonplanar.