2-Ethyl-1,3,4-trimethylimidazolium is a poor organic structure-directing agent in the synthesis of pure silica zeolites using fluoride as a mineralizer at 150 °C. Under these conditions only ill-crystallized solids are obtained after long hydrothermal treatments (several weeks). It disappoints despite its relatively large size, conformational rigidity, and intermediate hydrophilic/hydrophobic character, attributes which would qualify it as a promising structure-directing agent, according to prior investigations. By raising the crystallization temperature to 175 °C under otherwise identical conditions, crystallization is dramatically accelerated. Depending on the water/silica ratio and crystallization time, two different materials are obtained: the recently reported pure silica polymorph of the chiral STW-type zeolite, HPM-1, and the new layered organosilicate, HPM-2. Prolonged heating transforms these phases into the small-pore ITW-type zeolite, while no signs of the SOF-type zeolite (formally built from the same layers as STW) was found. A complete physicochemical and structural characterization of the as-made chiral HPM-1 zeolite is provided, and the proposed stabilization of this zeolite by polarization of the Si–O bond is supported by the observed deviation from tetrahedrality. HPM-1 is optically active, and a study of several crystallites by Mueller matrix microscopy shows that their optical activity can be individually measured and that this technique could be useful for the assessment of the enantiomeric purity of a microcrystalline powder.

A microporous polymorph of SiO(2), HPM-1, has a chiral structure and contains helical pores. The defect-free pure SiO(2) composition, which has been previously considered unfeasible for this structure type, bestows a high thermal and hydrothermal stability upon this material.

Pure silica ITW zeolite can be synthesized using 1,2,3-trimethylimidazolium and 1,3-dimethylimidazolium cations and fluoride anions as structure-directing agents (SDAs). Similarly to the previously reported 1,3,4-trimethylimidazolium, the dimethyl cation can also produce the zeolite TON, but this higher framework density phase finally transforms in situ into ITW. The structures of the as-made and calcined phases prepared with the new cations show a unit cell doubling along z, and the refined structures are reported. Periodic Density Functional Theory calculations provide the energies of the six SDA-ITW and SDA-TON zeolites, and their relative stabilities fully agree with the experimental observations. Structure-direction in this system is discussed from experimental and theoretical results that give strong support to the idea that strained silica frameworks are made possible in fluoride media by decreasing the covalent character of the Si-O bond. This decreased covalency is enhanced with the 1,2,3-trimethyl isomer, which is shown to be the strongest SDA for ITW and, at the same time, is the more hydrophilic of the three SDAs tested. Our observations with the three SDAs agree with the so-called Villaescusa's rule, i.e., the low framework density phase is favored at higher concentrations, but at the same time question the supersaturation hypothesis that has been proposed to explain this rule, since here the low-density phase is the most stable one.

HPM-2 is a new organosilicate layered material synthesized by the fluoride route using 2-ethyl-1,3,4trimethylimidazolium. The layers are of a new structural type (denoted mtf) and are held together by strong hydrogen bonds giving rise to a 1 H magic angle spinning (MAS) nuclear magnetic resonance (NMR) at around 16 ppm and by Coulombic interactions between silanolates and the organic cations residing in the interlayer space. Upon calcination HPM-2 transforms into the pure silica MTF zeolite by topotactic condensation, a process that is essentially completed at 400 °C. Attempts to apply known methods to derive new materials (swelling, delamination, interlayer expansion) are described. In the case of the interlayer expansion reaction, a nonmicroporous dense phase is obtained, which is likely due to an unfavorable disposition of silanols in close couples within each layer. Silanol condensation between the newly incorporated silicon species occurs across the main window producing narrower (6 member ring, 6MR) rather than wider (10MR) windows.