TY - JOUR
T1 - MX-Chain compounds with ReO4 counterions
T2 - Exploration of the robin-day class I-II boundary
AU - Kumagai, Shohei
AU - Takaishi, Shinya
AU - Gao, Mengqi
AU - Iguchi, Hiroaki
AU - Breedlove, Brian K.
AU - Yamashita, Masahiro
N1 - Funding Information:
This work was partially supported by the Asahi Glass Foundation, a JSPS KAKENHI grant (A) 26248015, grant (C) 16K05713, CREST (JST), and Tohoku University Molecule and Material Synthesis Platform in Nanotechnology platform project sponsored by the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan.
Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/4/2
Y1 - 2018/4/2
N2 - MX chains have been widely studied as a 1D mixed-valence system. Although there have been a large number of studies on the boundary between class II and III materials of the Robin-Day classification, there are few studies of compounds at the boundary between classes I and II. In this study, we synthesized a series of Pt- and Pd- MX-chain compounds with perrhenate counterions, [M(en)2][M(en)2X2](ReO4)4 (X = Br for M = Pd and X = Cl, Br, and I for M = Pt). All compounds were isostructural, and the metal-metal distances within the chain exceed 6 Å, which is the longest among MX-chain compounds thus far reported. For [Pt(en)2][Pt(en)2Cl2](ReO4)4 (PtCl), an intervalence charge transfer (IVCT) transition was observed in the UV region at 335 nm (3.7 eV), which is the shortest wavelength for the MX-chain compounds thus far reported, indicating that PtCl is the closest to the Robin-Day class I limit.
AB - MX chains have been widely studied as a 1D mixed-valence system. Although there have been a large number of studies on the boundary between class II and III materials of the Robin-Day classification, there are few studies of compounds at the boundary between classes I and II. In this study, we synthesized a series of Pt- and Pd- MX-chain compounds with perrhenate counterions, [M(en)2][M(en)2X2](ReO4)4 (X = Br for M = Pd and X = Cl, Br, and I for M = Pt). All compounds were isostructural, and the metal-metal distances within the chain exceed 6 Å, which is the longest among MX-chain compounds thus far reported. For [Pt(en)2][Pt(en)2Cl2](ReO4)4 (PtCl), an intervalence charge transfer (IVCT) transition was observed in the UV region at 335 nm (3.7 eV), which is the shortest wavelength for the MX-chain compounds thus far reported, indicating that PtCl is the closest to the Robin-Day class I limit.
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U2 - 10.1021/acs.inorgchem.7b03051
DO - 10.1021/acs.inorgchem.7b03051
M3 - Article
C2 - 29542925
AN - SCOPUS:85044938181
SN - 0020-1669
VL - 57
SP - 3775
EP - 3781
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 7
ER -