Observation of an Alternate Charge-Polarization State in a One-Dimensional Pt-Pt-I Chain Compound with a Bulky Pendant Ligand
Observation of an Alternate Charge-Polarization State in a One-Dimensional Pt-Pt-I Chain Compound with a Bulky Pendant Ligand
复制标题
具有大体积悬垂配体的一维 Pt-Pt-I 链化合物中交替电荷极化状态的观察
DOI：
10.1002/anie.202214108
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
H. Kitagawa
中科院分区：
文献类型：
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作者：
H. Moriyama;K. Otsubo;K. Sugimoto;S. Kawaguchi;H. Kitagawa
一维（1D）卤素桥联双核金属配合物（MMX-链）基于混合价金属二聚体体系表现出各种电子态。 本报告涉及一种新的MMX-链的合成和物理性质与庞大的侧配体，Pt 2（mcc-HexCS 2）4 I（mcc-HexCS 2 =反式-4-（甲氧羰基）环己烷二硫代羧酸酯）。由庞大的取代基引起的空间位阻在其一维链中引起应变，在环境条件下实现第一个纯交替电荷极化（ACP）状态（− Pt 2 +− Pt 3 +−I−− Pt 3 +− Pt 2 +−I−−），这是一种自旋佩尔斯态，通过X射线衍射及其导电和磁性特性证实。应变效应还表现为沿链方向的非常大的线性热膨胀沿着，这与没有大体积配体的常规MMX-链完全不同。具有配体变化的低维材料的设计预计将导致新的电子-晶格耦合电子态的出现。
A one‐dimensional (1D) halogen‐bridged dinuclear‐metal complex (MMX‐chain) exhibits various electronic states based on a mixed‐valence metal‐dimer system. This report deals with the synthesis and physical properties of a new MMX‐chain with a bulky pendant ligand, Pt2(mcc‐HexCS2)4I (mcc‐HexCS2=trans‐4‐(methoxycarbonyl)cyclohexanedithiocarboxylate). The steric hindrance caused by the bulky substituent induces a strain in its 1D chain, achieving at ambient condition the first pure alternate charge‐polarization (ACP) state (−Pt2+−Pt3+−I−−Pt3+−Pt2+−I−−), a kind of spin‐Peierls state, as confirmed by X‐ray diffraction and its conducting and magnetic properties. The strain effect is also manifested as a very large linear thermal expansion along the chain direction, which is quite different from conventional MMX‐chains without a bulky ligand. The design of low‐dimensional materials with ligand variations is expected to lead to the emergence of new electron–lattice coupled electronic states.