Expanding the frequency range of the solid-state T1rho experiment for heteronuclear dipolar relaxation

Solid-state spin–lattice relaxation in the rotating frame permits the investigation of dynamic processes with correlation times in the range of microseconds. The relaxation process in organic solids is driven by the fluctuation of the local magnetic field due to the dipole–dipole interaction of the probe nuclei (¹³C,¹⁵N) with ¹H in close proximity. However, its effect is often hidden by a competing relaxation process due to the contact between the rotating frame ¹³C/¹⁵N Zeeman and ¹H dipolar reservoirs. In most cases the latter process becomes superior for the commonly applied low and moderate spin-lock fields and practically does not provide information about the molecular dynamics. To suppress this undesired process and to expand the dynamic range of T_{1 ρ} experiments, we present two approaches. The first one uses a resonance offset of the frequency of the spin-lock irradiation, which leads to a significant enhancement of the effective spin-lock frequency without the application of destructive high transmitter powers. We derive the theory and demonstrate the applicability of the method on various model compounds. The second approach utilizes heteronuclear ¹H decoupling during the ¹³C/¹⁵N spin-lock irradiation which disrupts the contact between the ¹³C/¹⁵N Zeeman and ¹H dipolar reservoirs. We demonstrate the method and discuss the results qualitatively.