Solid-state NMR experiments were performed on a Bruker 500 MHz (B0= 11.75 T) Avance NEO NMR spectrometer, equipped with a 4 mm double resonance HX magic-angle spinning (MAS) Bruker probe. Powdered samples were diluted (50% by mass with dry silica) and packed into 4 mm o.d. zirconia ceramic rotors and sealed with a Vespel ® cap inside an Ar glove box. Li MAS NMR data were acquired using a Bloch decay pulse sequence with optimized pulse widths between 3.3 and 4.0 µs (calibrated for each sample, B1/2 = 71 kH (sol ion)), rec cle delays of 5 20 s, 16 co-added transients and a spinning frequency of 10 kHz. Variable temperature non-spinning Li NMR using a Bloch decay and inversion recovery pulse sequences were used to measure the linewidth (fwhm) and nuclear spin-lattice relaxation (T1), respectively, between 203 and 333 K. Acquisition parameters were identical to those reported above. The Li NMR spectra were referenced to 0 ppm using 1 M LiCl solution. Non-spinning 121 Sb NMR meas remen s ere acq ired sing a Hahn echo ( /2 acq.) pulse sequence, with 2 and 4 µs pulses ( B1/2 = 42 kH (sol ion)), be een 2k and 100k co-added transients and recycle delays of 0.25 1 s. For 121 Sb NMR spectra of Li2Sb and Li3SbxBi1-x compounds the variable offset cumulative spectrum (VOCS) approach was applied using 50-100 kHz offsets and between 3 and 10 steps. The 121 Sb NMR spectra were referenced to 0 ppm using 0.5 M KSbF6 in acetonitrile. The non-spinning 209 Bi NMR spectrum of Li3Bi was collected using a Bloch decay p lse seq ence i h a /2 = 3.2 s, 128 co-added transients and a 1 s recycle delay. The 209 Bi NMR data was referenced to 0 ppm using a saturated solution of Bi(NO3)3 in HNO3 and D2O.