High-resolution solid-state NMR of quadrupolar nuclei.
We report the observation of high-resolution solid-state NMR spectra of (23)Na (I = [unk]), (27)Al (I = [unk]) and (51)V (I = [unk]) in various inorganic systems. We show that, contrary to popular belief, relatively high-resolution ( approximately 10 ppm linewidth) spectra may be obtained from quadrupolar systems, in which electric quadrupole coupling constants (e(2)qQ/h) are in the range approximately 1-5 MHz, by means of observation of the ((1/2), -(1/2)) spin transition. The ((1/2), -(1/2)) transition for all nonintegral spin quadrupolar nuclei (I = [unk], [unk], [unk], or [unk]) is only normally broadened by dipolar, chemical shift (or Knight shift) anisotropy or second-order quadrupolar effects, all of which are to a greater or lesser extent averaged under fast magic-angle sample rotation. In the case of (23)Na and (27)Al, high-resolution spectra of (23)NaNO(3) (e(2)qQ/h approximately 300 kHz) and alpha-(27)Al(2)O(3) (e(2)qQ/h approximately 2-3 MHz) are presented; in the case of (51)V(2)O(5) (e(2)qQ/h approximately 800 kHz), rotational echo decays are observed due to the presence of a approximately 10(3)-ppm chemical shift anisotropy. The observation of high-resolution solid-state spectra of systems having spins I = [unk], [unk], and [unk] in asymmetric environments opens up the possibility of examining about two out of three nuclei by solid-state NMR that were previously thought of as "inaccessible" due to the presence of large (a few megahertz) quadrupole coupling constants. Preliminary results for an I = [unk] system, (93)Nb, having e(2)qQ/h approximately 19.5 MHz, are also reported.
School of Chemical Sciences, University of Illinois at Urbana-Champaign, 505 South Mathews Avenue, Urbana, Illinois 61801.
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Meadows
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Smith
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Kinsey
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Rothgeb
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Skarjune
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Oldfield