Spin and molecular dynamics in acyl-containing biradicals: Time-resolved electron paramagnetic resonance and laser flash photolysis study

A combination of time-resolved electron paramagnetic resonance (TREPR) and laser flash photolysis (LFP) studies of flexible acyl-containing biradicals over a wide temperature range is reported. In contrast to previous reports, it is shown that the main channel of intersystem crossing in these biradicals is the electron spin relaxation of the acyl moiety rather than spin-orbit interaction in the biradical. This relaxation determines the decay rate of the electron spin polarization at low temperatures and the biradical lifetime at high temperatures. The relaxation mechanism is attributed to the spin-rotation interaction, associated with the rotation of the carbonyl group about the neighboring C-C bond axis. From a model simulation of the time profile of the spin-polarized TREPR signal based on the numerical solution of the stochastic Liouville equation of the spin density matrix in frame of realistic model of biradical, the Arrhenius parameters for correlation times of spin rotation interaction and activation energies for molecular and spin dynamics were determined in two solvents, 2-propanol and hexane.