Isomeric effects on the acidity of Al₁₃ Keggin clusters in porous ionic crystals

Abstract

We demonstrate a facile synthesis method of a porous ionic crystal (PIC) composed of the little-known δ-Keggin-type cationic polyoxoaluminum cluster ([δ-Al₁₃O₄(OH)₂₄(H₂O)₁₂]⁷⁺, δ-Al₁₃) with an oppositely-charged polyoxometalate, which enabled us to investigate the activity as a solid acid. The δ-Al₁₃ based PIC exhibited much higher activity in pinacol rearrangement, a typical acid-catalyzed reaction, than the PIC based on the well-known and thermodynamically stable rotational isomer (ε-Al₁₃). This work is a rare example of rotational isomers of polyoxoaluminum clusters exhibiting remarkably different catalytic activities.