Porous Ionic Crystals Modified by Post-Synthesis of K2[Cr3O(OOCH)6(etpy)3]2[α-SiW12O40]·8H2O through Single-Crystal-to-Single-Crystal Transformation

• Published in: Inorganic chemistry 2013-08, Vol.52 (16), p.9320-9326
• Main Authors: Uchida, Sayaka, Takahashi, Eri, Mizuno, Noritaka
• Format: Article
• Language: English
• Subjects: Chromium - chemistry; Models, Molecular; Organometallic Compounds - chemical synthesis; Organometallic Compounds - chemistry; Particle Size; Porosity; Potassium - chemistry; Surface Properties; Tungsten - chemistry
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic4008334

Post-synthesis modification of a porous ionic crystal proceeded via two steps (acid treatment followed by ion-exchange) in an aqueous solution and a single-crystal-to-single-crystal manner. Compound K2[Cr3O(OOCH)6(etpy)3]2[α-SiW12O40]·8H2O (etpy = 4-ethylpyridine) [1a] is a porous ionic crystal with one-dimensional channels, which can accommodate guests such as water, alcohols, and halocarbons. Crystals of 1a were immersed in an aqueous HCl solution (acid treatment), and the etpy ligand which was exposed to the one-dimensional channel was removed and exchanged with water. The formula of the resulting compound was (etpyH+)2[Cr3O(OOCH)6(etpy)2(H2O)]2[α-SiW12O40]·6H2O [2a], and K+ ions, which are potential guest binding sites, were simultaneously removed by this treatment. Reincorporation of K+ ions was attempted by immersion of 2a into an aqueous CH3COOK solution (ion-exchange), and K2[Cr3O(OOCH)6(etpy)2.5(H2O)0.5]2[α-SiW12O40]·8H2O [3a] was formed. Increase in sorption capacity by the two-step post-synthesis modification was confirmed by sorption isotherms and Monte Carlo-based simulations using water as a probe molecule. The role of K+ ions as water binding sites was confirmed by water sorption isotherms of alkali metal ion-exchanged compounds.