Electron spin relaxation of a boron-containing heterocyclic radical

Preparation of the stable boron-containing heterocyclic phenanthrenedione radical, (C₆F₅)₂B(O₂C₁₄H₈), by frustrated Lewis pair chemistry has been reported recently. Electron paramagnetic resonance measurements of this radical were made at X-band in toluene:dichloromethane (9:1) from 10 to 293K, in toluene from 180 to 293K and at Q-band at 80K. In well-deoxygenated 0.1mM toluene solution at room temperature hyperfine splittings from ¹¹B, four pairs of ¹H, and 5 pairs of ¹⁹F contribute to an EPR spectrum with many resolved lines. Observed hyperfine couplings were assigned based on DFT calculations and account for all of the fluorines and protons in the molecule. Rigid lattice g values are g_x=2.0053, g_y=2.0044, and g_z=2.0028. Near the melting point of the solvent 1/T_m is enhanced due to motional averaging of g and A anisotropy. Increasing motion above the melting point enhances 1/T₁ due to contributions from tumbling-dependent processes. The overall temperature dependence of 1/T₁ from 10 to 293K was modeled with the sum of contributions of a process that is linear in T, a Raman process, spin rotation, and modulation of g anisotropy by molecular tumbling. The EPR measurements are consistent with the description of this compound as a substituted aromatic radical, with relatively small spin density on the boron.