MX-chain Compounds with ReO4 Counterions: Exploration of the Robin-Day Class I-II Boundary
MX-chain Compounds with ReO4 Counterions: Exploration of the Robin-Day Class I-II Boundary
复制标题
具有 ReO4 抗衡离子的 MX 链化合物：Robin-Day I-II 类边界的探索
DOI：
10.1021/acs.inorgchem.7b03051
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发表时间：
2018
期刊：
影响因子：
4.6
通讯作者：
Masahiro Yamashita
中科院分区：
文献类型：
--
作者：
Shohei Kumagai;Shinya Takaishi;Mengqi Gao;Hiroaki Iguchi;Brian K. Breedlove;Masahiro Yamashita
MX链作为一种一维混价体系被广泛研究。虽然对Robin-Day分类中II类和III类物质边界的研究较多，但对I类和II类化合物边界的研究较少。在这项研究中，我们合成了一系列Pt-和Pd- mx -链化合物，具有过透酸反离子[M(en)2][M(en)2X2](ReO4)4（M = Pd时X = Br, M = Pt时X = Cl， Br和I）。所有化合物均为同构，链内金属-金属距离超过6 Å，是目前报道的mx链化合物中最长的。对于[Pt(en)2][Pt(en)2Cl2](ReO4)4(PtCl)，在335 nm （3.7 eV）的紫外区观察到价间电荷转移（IVCT）跃迁，这是迄今为止报道的mx链化合物的最短波长，表明ptclis最接近Robin-Day I类极限。
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 thatPtClis the closest to the Robin–Day class I limit.