Observation of proximities between spin-1/2 and quadrupolar nuclei in solids: Improved robustness to chemical...

We introduce a novel heteronuclear dipolar recoupling based on the R2₁^-1 symmetry, which uses the tanh/tan (tt) shaped pulse as a basic inversion element and is denoted R2₁^-1(tt). Using first-order average Hamiltonian theory, we show that this sequence is non-γ-encoded and that it reintroduces the |m| = 1 spatial component of the Chemical Shift Anisotropy (CSA) of the irradiated isotope and its heteronuclear dipolar interactions. Using numerical simulations and one-dimensional (1D) ²⁷Al-{³¹P} through-space D-HMQC (Dipolar Heteronuclear Multiple-Quantum Correlation) experiments on VPI-5, we compare the performances of this recoupling to those of other non-γ-encoded |m| = 1 heteronuclear recoupling schemes: REDOR (Rotational-Echo DOuble Resonance), SFAM (Simultaneous Frequency and Amplitude Modulation) and R4₂^-1(tt). Such comparison indicates that the R2₁^-1(tt) scheme is more robust to CSA, offset and radiofrequency field inhomogeneities than the other schemes. We take advantage of the high robustness of R2₁^-1(tt) to CSA and offset to demonstrate the possibility to correlate the signals of ²⁰⁷Pb isotope with those of neighboring half-integer spin quadrupolar nuclei. Such approach is demonstrated experimentally by acquiring ¹¹B-{²⁰⁷Pb} D-HMQC 2D spectra of Pb₄O(BO₃)₂ crystalline powder.