31P MAS refocused INADEQUATE spin-echo (REINE) NMR spectroscopy: revealing J coupling and chemical shift...

Two-dimensional (2D) variations in (2)J(P(1),P(1)), (2)J(P(1),P(2)), and (2)J(P(2),P(2)) are obtained--using the REINE (REfocused INADEQUATE spin-Echo) pulse sequence presented by Cadars et al. (Phys. Chem. Chem. Phys. 2007, 9, 92-103)--from pixel-by-pixel fittings of the spin-echo modulation for the 2D correlation peaks due to linked phosphate tetrahedra (P(1)-P(1), P(1)-P(2), P(2)-P(1), and P(2)-P(2)) in a (31)P refocused INADEQUATE solid-state MAS NMR spectrum of a cadmium phosphate glass, 0.575CdO-0.425P(2)O(5). In particular, separate variations for each 2D (31)P REINE peak are obtained which reveal correlations between the J couplings and the (31)P chemical shifts of the coupled nuclei that are much clearer than those evident in previously presented 2D z-filtered (31)P spin-echo spectra. Notably, such correlations between the J couplings and the (31)P chemical shifts are observed even though the conditional probability distributions extracted using the protocol of Cadars et al. (J. Am. Chem. Soc. 2005, 127, 4466-4476) indicate that there is no marked correlation between the (31)P chemical shifts of neighboring phosphate tetrahedra. For 2D peaks at the P(2) (31)P chemical shift in the direct dimension, there can be contributions from chains of three units (P(1)-P(2)-P(1)), chains of four units (P(1)-P(2)-P(2)-P(1)), or longer chains or rings (-P(2)-P(2)-P(2)-): for the representative glass considered here, best fits are obtained assuming a glass comprised predominantly of chains of four units. The following variations are found: (2)J(P(1),P(1)) = 13.4 +/- 0.3 to 14.8 +/- 0.5 Hz, (2)J(P(1),P(2)) = 15.0 +/- 0.3 to 18.2 +/- 0.3 Hz, and (2)J(P(2),P(2)) = 5.9 +/- 0.6 to 9.1 +/- 0.9 Hz from the fits to the P(1)-P(1), P(1)-P(2), and P(2)-P(2) peaks, respectively. The correlation of a particular J coupling with the (31)P chemical shifts of the considered nucleus and the coupled nucleus is quantified by the coefficients C(F(2)) and C(F(1)) that correspond to the average pixel-by-pixel change in the J coupling with respect to the chemical shift of the observed (F(2)) and neighboring (F(1)) (31)P nuclei, respectively.