On the synthetic front, Barnes et al. have developed a two-step non-hydrolytic solgel procedure for the preparation of microporous metallosilicates under mild conditions. In this work, we concentrated on the first step of the synthetic method described by Styskalik et al. to obtain a series of sparse, amorphous, statistically connected aluminosilicate networks (oligomers) containing [L- AlO 3 ] and [AlO 4 ] -sites (L = tetrahydrofuran (THF), pyridine (py), triethylamine (Et 3 N) or triethylphosphine oxide (TEPO)). The CUBE building block was reacted with a limited amount of L-AlCl3, L-AlMe3, L-AlEt 3 , or [Me 4 N] [AlCl 4 ] in toluene and THF (Figure ). The major emphasis of this investigation was placed on the identification of well-defined structural units in these materials and their characterization by Al TQ/MAS NMR techniques in order to extract their spectroscopic parameters -the isotropic chemical shift (δ iso ), the quadrupole coupling constant (CQ), and the asymmetry parameter (η). The chosen palette of ligands provides a range of site symmetries and coordination strengths for the purpose of correlating their effect on the synthesis and spectroscopic parameters. The effects of the local disorder can be studied in comparisons of materials with two different Al loadings, leading to varying extents of cross-linking and thereby different levels of conformational freedom for the sites. The experimentally determined NMR parameters were compared to the values predicted by DFT calculations on the corresponding fully-relaxed, truncated models in order to provide a sound assignment to the experimental spectra as well as to establish a correlation of the C Q parameter with the site symmetry. The insight gained from this investigation should provide more clarity to the assignment of Al solid-state NMR spectra of the more opaque, real-world systems, such as the aforementioned activated zeolites. Finally, a reaction mechanism is proposed for a side-reaction generating [AlO4] -sites.