The effect of Magic Angle Spinning on proton spin–lattice relaxation times in some organic solids

Proton spectra of solids are usually broadened by strong proton homonuclear dipolar interactions. However, substantial line narrowing may be achieved by Magic Angle Spinning (MAS) in systems of low proton density or in systems in which rapid molecular motions occur. In such conditions, T₁(H) measurements are often used to characterise the dynamics of each resolved proton site. We show that T₁(H) values measured for solid organic compounds with high proton abundance, such as adamantane and glycine, may be strongly dependent on the spinning rate employed, so that care is required when values are compared. The effects of molecular motion and proton density on T₁(H) and its dependence on spinning rate were investigated. We found that an increase in molecular motion leads to an increase of T₁(H) at higher spinning rates. The opposite is found for systems with low proton densities which show relatively lower T₁(H), at higher spinning rates. A possible interpretation is suggested in terms of the reduced spin diffusion efficiency at higher spinning rates.