The first step of the non-hydrolytic sol-gel procedure of Styskalik et al., as described in the experimental details, was used with the aim to produce single-site materials containing exclusively L-Al(OCUBE)3 (L = THF, Et3N, py, TEPO) or [Me 4 N] + [Al(OCUBE) 4 ] -sites. The molecular spherosilicate building block CUBE was cross-linked by limited amounts of L-AlCl3, L-AlMe3, L-AlEt3, or [Me4N] [AlCl4], affording sparse, statistically linked networks -oligomers (Table ). Reactions 1-5 and 7-16 produced non-porous glassy solids that could be reversibly redissolved into colloidal viscous solutions, indicating the oligomeric character of the formed species. Reaction 6 produced a gel upon heating and subsequently an insoluble porous (126 m 2 g -1 ) solid upon drying, indicating an even higher extent of cross-linking leading to the formation of an extended 3D network. In the following discussion, the same numbering system refers to both reactions and the resulting materials (products).