A Coordination Network with Ligand-Centered Redox Activity Based on facial-[CrIII (2-mercaptophenolato)3 ]3- Metalloligands

Masanori Wakizaka; Takeshi Matsumoto; Atsushi Kobayashi; Masako Kato; Ho-Chol Chang

doi:10.1002/chem.201701613

A Coordination Network with Ligand-Centered Redox Activity Based on facial-[Cr^III (2-mercaptophenolato)₃ ]^3- Metalloligands

Chemistry. 2017 Jul 21;23(41):9919-9925. doi: 10.1002/chem.201701613. Epub 2017 Jun 29.

Authors

Masanori Wakizaka^{1

2}, Takeshi Matsumoto¹, Atsushi Kobayashi², Masako Kato², Ho-Chol Chang¹

Affiliations

¹ Department of Applied Chemistry, Faculty of Science and Engineering, Chuo University, 1-13-27 Kasuga, Bunkyo-ku, Tokyo, 112-8551, Japan.
² Department of Chemistry, Faculty of Science, Hokkaido University, North-10, West-8, Kita-ku, Sapporo, 060-0810, Japan.

PMID: 28556286
DOI: 10.1002/chem.201701613

Abstract

The design of redox-active metal-organic frameworks and coordination networks (CNs), which exhibit metal- and/or ligand-centered redox activity, has recently received increased attention. In this study, the redox-active metalloligand (RML) [Me₄ N]₃ fac-[Cr^III (mp)₃ ] (1) (mp=2-mercaptophenolato) was synthesized and characterized by single-crystal X-ray diffraction analysis, and its reversible ligand-centered one-electron oxidation was examined by cyclic voltammetry and spectroelectrochemical measurements. Since complex 1 contains O/S coordination sites in three directions, complexation with K⁺ ions led to the formation of the two-dimensional honeycomb sheet-structured [K₃ fac-{Cr^III (mp)₃ }(H₂ O)₆ ]_n (2⋅6 H₂ O), which is the first example of a redox-active CN constructed from a RML with o-disubstituted benzene ligands. Herein, we unambiguously demonstrate the ligand-centered redox activity of the RML within the CN 2⋅6 H₂ O in the solid state.

Keywords: anions; coordination network; mercaptophenolato ligand; metalloligand; redox chemistry.