Abstract
Gallium model systems containing four‐ and six‐coordinate gallium sites have been investigated using solid‐state NMR. Measurement of the isotropic chemical shift and electric field gradient (EFG) have been performed at 9.4 T on α‐Ga~2~O~3~, β‐Ga~2~O~3~, LiGaO~2~, NaGaO~2~, KGaO~2~, Ga~2~(SO~4~)~3~, and LaGaO~3~ using a variety of techniques on both NMR active nuclei (^69^Ga and ^71^Ga) including static, high speed magic‐angle spinning (MAS), satellite transition (ST) spectroscopy, and rotor‐assisted population transfer (RAPT). The chemical shift is found to correlate well with the coordination number, with four‐coordinate gallium having values of approximately 50 ppm and six‐coordinate gallium having values near 225 ppm (referenced to 1 M gallium nitrate solution). The magnitude of the EFG is found to be correlated to the distortion of the gallium polyhedra, with the strained systems having EFGs of 3 × 10^21^ Vm^−2^ or more, while the less strained systems have values of 1.5 × 10^21^ Vm^−2^ or less. A plot of chemical shift versus EFG suggests that solid‐state NMR of gallium oxyanions can be more discriminating than liquid state NMR chemical shifts alone. Copyright © 2006 John Wiley & Sons, Ltd.