TY - JOUR
T1 - A Coordination Network with Ligand-Centered Redox Activity Based on facial-[CrIII(2-mercaptophenolato)3]3− Metalloligands
AU - Wakizaka, Masanori
AU - Matsumoto, Takeshi
AU - Kobayashi, Atsushi
AU - Kato, Masako
AU - Chang, Ho Chol
N1 - Funding Information:
We would like to acknowledge Prof. Dr. Tamejiro Hiyama and Dr. Yasunori Minami (Chuo University), as well as Prof. Dr. Youichi Ishii and Dr. Shintaro Kodama (Chuo University) for their support with crystallographic measurement and elemental analyses, respectively. Moreover, we are also grateful to Dr. Ulrich Mayer for his helpful suggestions on the manuscript. This work was supported financially by MEXT KAKENHI grants 16K13967, 16H04123, and 26620050, as well as JSPS KAKENHI grants 262494 and JP16H06509 (Coordination Asymmetry), and the Creative Research Institution (CRIS), Hokkaido Univ.
Publisher Copyright:
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2017/7/21
Y1 - 2017/7/21
N2 - 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) [Me4N]3fac-[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 [K3fac-{CrIII(mp)3}(H2O)6]n (2⋅6 H2O), 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 H2O in the solid state.
AB - 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) [Me4N]3fac-[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 [K3fac-{CrIII(mp)3}(H2O)6]n (2⋅6 H2O), 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 H2O in the solid state.
KW - anions
KW - coordination network
KW - mercaptophenolato ligand
KW - metalloligand
KW - redox chemistry
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U2 - 10.1002/chem.201701613
DO - 10.1002/chem.201701613
M3 - Article
C2 - 28556286
AN - SCOPUS:85025070522
VL - 23
SP - 9919
EP - 9925
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 41
ER -