The precise pore sizes defined by crystalline zeolite lattices have led to intensive research on zeolite membranes. Unfortunately, zeolites have been extremely difficult to prepare in a defect-free thin film form needed for membrane flux and selectivity. We introduced tetrapropylammonium (TPA), a structure-directing agent for zeolite ZSM-5, into a silica sol and exploit the development of high solvation stresses to create templated amorphous silicas with pore apertures similar in size to those of ZSM-5. Silicon and carbon NMR experiments were performed to evaluate the efficacy of our templating approach. The Si-29 NMR spectrum of the silica matrix was observed by an intermolecular cross-polarization experiment involving the H-1 nuclei of TPA and the Si-29 nuclei in the silica matrix. The efficiency of the cross-polarization interaction was used to investigate the degree to which the matrix formed a tight cage surrounding the template molecule. Bulk xerogels, prepared by gelation and slow drying of the corresponding sols, exhibited only weak interactions between the two sets of nuclei. Thin film xerogels, where drying stresses are greater, exhibited significantly increased interactions. Intramolecular cross-polarization experiments between the H-1 and C-13 nuclei of the template molecule demonstrated that much of the increased efficiency was a result of reduced rotational mobility of the TPA molecule.