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A Coordination Network with Ligand-Centered Redox Activity Based on facial-[CrIII (2-mercaptophenolato)3 ]3-
Masanori Wakizaka1,2, Takeshi Matsumoto1, Atsushi Kobayashi2
1Department of Applied Chemistry, Faculty of Science and Engineering, Chuo University, 1-13-27 Kasuga, Bunkyo-ku, Tokyo, 112-8551, Japan.
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-[CrIII (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-{CrIII (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.
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