An Aluminosilicate Zeolite Containing Rings of Tetrahedral Atoms with All Odd Numbers from Five to Eleven.

Herein we report the synthesis, structure solution, and catalytic properties of PST‐31, which has an unprecedented framework topology. This high‐silica (Si/Al=16) zeolite was synthesized using a pyrazolium‐based dication with a tetramethylene linker as an organic structure‐directing agent (OSDA) in hydroxide media. The PST‐31 structure is built from new building layers containing four‐, five‐, six‐, and seven‐membered rings, which are connected by single four‐membered rings in the interlayer region to form a two‐dimensional pore system. Its channels consist of [4.56.6.9.11] and [5.6.7.9.10.11] cavities and are thus delimited by nine‐, ten‐, and eleven‐membered rings. The OSDA cations in as‐synthesized PST‐31 were determined to reside without disorder in the large [42.514.64.72.94] cavities composed of smaller [4.56.6.9.11] and [5.6.7.9.10.11] ones, leading to a symmetry coincidence between the OSDA and the surrounding zeolite cavity. The proton form of PST‐31 was found to be selective for the cracking of n‐hexane to light olefins. [ABSTRACT FROM AUTHOR]