Heterogeneous catalase-like activity of gold(i)-cobalt(iii) metallosupramolecular ionic crystals

Mihoko Yamada; Nobuto Yoshinari; Naoto Kuwamura; Toru Saito; Satoshi Okada; Sai Prakash Maddala; Koji Harano; Eiichi Nakamura; Kohei Yamagami; Keisuke Yamanaka; Akira Sekiyama; Tomoyoshi Suenobu; Yusuke Yamada; Takumi Konno

doi:10.1039/c6sc04993a

Heterogeneous catalase-like activity of gold(i)-cobalt(iii) metallosupramolecular ionic crystals

Chem Sci. 2017 Apr 1;8(4):2671-2676. doi: 10.1039/c6sc04993a. Epub 2017 Jan 16.

Authors

Affiliations

¹ Department of Chemistry , Graduate School of Science , Osaka University , Toyonaka , Osaka 560-0043 , Japan . Email: konno@chem.sci.osaka-u.ac.jp.
² Department of Biomedical Information Sciences , Graduate School of Information Sciences , Hiroshima City University , Asa-Minami-ku , Hiroshima 731-3194 , Japan.
³ Department of Chemistry , Graduate School of Science , The University of Tokyo , Bunkyo-ku , Tokyo 113-0033 , Japan.
⁴ Division of Materials Physics , Graduate School of Engineering Science , Osaka University , Toyonaka , Osaka 560-8531 , Japan.
⁵ Synchrotron Radiation Center , Ritsumeikan University , Kusatsu , Shiga 525-8577 , Japan.
⁶ Department of Material and Life Science , Graduate School of Engineering , Osaka University , ALCA and SENTAN , Japan Science and Technology (JST) , Suita , Osaka 565-0871 , Japan.
⁷ Department of Applied Chemistry & Bioengineering , Graduate School of Engineering , Osaka City University , Sumiyoshi-ku , Osaka 558-8585 , Japan.

Abstract

Unique heterogeneous catalase-like activity was observed for metallosupramolecular ionic crystals [Au^I₄Co^III₂(dppe)₂(d-pen)₄]X _n ([1]X _n ; dppe = 1,2-bis(diphenylphosphino)ethane; d-pen = d-penicillaminate; X _n = (Cl^-)₂, (ClO₄^-)₂, (NO₃^-)₂ or SO₄^2-) consisting of Au^I₄Co^III₂ complex cations, [1]²⁺, and inorganic anions, X^- or X^2-. Treatment of the ionic crystals with an aqueous H₂O₂ solution led to considerable O₂ evolution with a high turnover frequency of 1.4 × 10⁵ h^-1 for the heterogeneous cobalt complexes, which was dependent on their size and shape as well as the arrangement of cationic and anionic species. These dependencies were rationalized by the presence of cobalt(ii) centers on the crystal surface and their efficient exposure on the (111) plane rather than the (100) plane based on morphological and theoretical studies.