Impact of Chlorine Substitution on Electron Spin Relaxation of a Trityl Radical

A perchlorotriarylmethyl tricarboxylic acid radical 99% enriched in ¹³C at the central carbon (¹³C₁-PTMTC) was characterized in phosphate buffered saline solution (pH = 7.2) (PBS) at ambient temperature. Samples immobilized in 1:1 PBS:glycerol or in 9:1 trehalose:sucrose were studied as a function of temperature. Isotope enrichment at C₁ creates a trityl that can be used to accurately measure microscopic viscosity. Understanding of the impact of the ¹³C hyperfine interaction on electron spin relaxation is important for application of this trityl in oximetry and distance measurements. The anisotropic ¹³C₁ hyperfine couplings (A_x = A_y = 24 ± 2 MHz, A_z = 200 ± 1 MHz) are larger than for the related ¹³C₁-perdeuterated Finland trityl (¹³C₁-dFT) and the g anisotropy (g_x = 2.0013, g_y = 2.0016, g_z = 2.0042) is slightly larger than for ¹³C₁-dFT. The tumbling correlation times (τ_R) for ¹³C₁-PTMTC are 0.20 ± 0.02 ns in PBS and 0.40 ± 0.05 ns in 3:1 PBS:glycerol, which are shorter than for ¹³C₁-dFT in the same solutions. T₁ for ¹³C₁-PTMTC is 3.5 ± 0.5 μs in PBS and 5.3 ± 0.4 μs in 3:1 PBS:glycerol, which are shorter than for ¹³C₁-dFT due to faster tumbling, larger anisotropy of the ¹³C₁ hyperfine, and about 30% larger contribution from the local mode. In immobilized samples T₁ for ¹³C₁-PTMTC is similar to that for ¹³C₁-dFT and other trityls without chlorine or ¹³C₁ substituents, indicating that the ¹³C₁ and Cl substituents on the phenyl rings have little impact on T₁. The temperature dependence of T₁ was modeled with contributions from the direct, Raman, and local mode processes. Broadening of CW linewidths of about 0.6 G in fluid solution and about 2 G in rigid lattice is attributed to unresolved ^35,37Cl hyperfine couplings.