Due to their highly-ordered, crystalline nature, the three molecular analogs provide an ideal platform for studying the influence of local coordination and identity of ligand on the 71 Ga NMR signature in gallosilicate materials. In order to understand in more detail the relationship between structures and NMR signatures, DFT calculations were performed on the molecular systems 1-THF, 1-py and 1-TPPO (for details see SI S6), and their 71 Ga NMR spectra were obtained at the two different magnetic fields (14.1 and 21.15 T, Figure ). The 71 Ga solid-state NMR of 1-THF possesses a broad, complex lineshape consistent with Ga sites having large quadrupolar coupling constants (ca. 40 MHz)