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Updated: May 23, 2025
Controlling the Size, Shape and Stability of Supramolecular Polymers in Water
Published on: August 2, 2012
Size and Shape Effect of Countercations on Depolymerization and Water Oxidation Catalysis of Cyano-Bridged
Yusuke Seki1, Takashi Nakazono2, Yusuke Yamada1,2
1Chemistry and Bioengineering, Graduate School of Engineering, Osaka Metropolitan University, Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan.
Abstract:
A cyano-bridged coordination polymer (CP), K{CoII1.5[FeII(CN)6]} {(K)Co-Fe}, insoluble in water was successfully solubilized by countercation exchange with Me4N+ ions. On the one hand, the resultant powder remained insoluble after countercation exchange with NH4+ or Et4N+ ions. Powder X-ray diffraction measurements indicated that solubility was closely related to the crystal structures of the obtained powder after countercation exchange. The penetration of a countercation with an appropriate size into the Co-Fe framework resulted in solubilization by depolymerization. Countercation exchange with RMe3N+ ions (R = Et, n-Pr, or n-Bu), which have an orthogonal projection size similar to that of the Me4N+ ion, solubilized the Co-Fe framework. On the other hand, n-HexMe3N+ ions hardly penetrating the Co-Fe framework provided insoluble powder due to the longer alkyl chain. The solubilized cyano-bridged CPs exhibited higher catalytic activity for water oxidation.
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