Measuring distances between half-integer quadrupolar nuclei and detecting relative orientations of quadrupolar and dipolar tensors by double-quantum homonuclear dipolar recoupling nuclear magnetic resonance experiments

Abstract

We studied the possibility of using double-quantum homonuclear dipolar recoupling magic angle spinning nuclear magnetic resonance experiments for structural analysis of systems of half-integer quadrupolar nuclei. We investigated symmetry-based recoupling schemes R2(2) (1) and R2(2) (1)R2(2) (-1) and showed that the obtained double-quantum filtered signals depend substantially on magnitudes and relative orientations of dipolar and quadrupolar tensors. Experimental results measured on aluminophosphate molecular sieve AlPO(4)-14, containing dipolar-coupled spin-52 aluminum nuclei, were compared to results of time-consuming numerical simulations. The comparison for short mixing times allowed us to roughly measure internuclear Al-Al distances, if constraints about relative tensor orientations were available. Inspection of relative orientations of dipolar and quadrupolar tensors, using known distances between nuclei, required experimental and simulated data for long mixing times and yielded less accurate results. Two experimental protocols were employed for measuring double-quantum filtered curves, the symmetric protocol, in which excitation and reconversion periods are incremented simultaneously, and the asymmetric protocol, in which only the length of the excitation period is incremented and the length of the reconversion period is kept constant. The former experimental protocol was more convenient for the detection of internuclear distances, and the latter one was more appropriate for the inspection of relative orientations of interaction tensors.