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

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

来源：Chemistry - A European Journal, 2017, 23(41): 9919-9925.

DOI：10.1002/chem.201701613

• anions
• coordination network
• mercaptophenolato ligand
• metalloligand
• redox chemistry

The design of redox-active metal-organic frameworks and coordination networks (CNs), which exhibit metaland/or ligand-centered redox activity, has recently received increased attention. In this study, the redox-active metalloligand (RML) [Me4N](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 [K(3)fac{ Cr-III(mp)(3)}(H2O)(6)] n (2.6H(2)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 2.6H(2)O in the solid state.

• 出版日期2017-7-21