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锶钒氧化物-氢化物:“平面正方形”二电子相。

Strontium vanadium oxide-hydrides: "square-planar" two-electron phases.

机构信息

Department of Chemistry, Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, OX1 3QR (UK).

出版信息

Angew Chem Int Ed Engl. 2014 Jul 14;53(29):7556-9. doi: 10.1002/anie.201403536. Epub 2014 Jun 24.

Abstract

A series of strontium vanadium oxide-hydride phases prepared by utilizing a low-temperature synthesis strategy in which oxide ions in Sr(n+1)V(n)O(3n+1) (n=∞, 1, 2) phases are topochemically replaced by hydride ions to form SrVO2H, Sr2VO3H, and Sr3V2O5H2, respectively. These new phases contain sheets or chains of apex-linked V(3+)O4 squares stacked with SrH layers/chains, such that the n=∞ member, SrVO2H, can be considered to be analogous to "infinite-layer" phases, such as Sr(1-x)Ca(x)CuO2 (the parent phase of the high-T(c) cuprate superconductors), but with a d(2) electron count. All three oxide-hydride phases exhibit strong antiferromagnetic coupling, with SrVO2H exhibiting an antiferromagnetic ordering temperature, T(N)>300 K. The strong antiferromagnetic couplings are surprising given they appear to arise from π-type magnetic exchange.

摘要

利用低温合成策略制备了一系列锶钒氧化物-氢化物相,其中 Sr(n+1)V(n)O(3n+1)(n=∞,1,2)相中的氧离子通过拓扑化学反应被氢化物离子取代,分别形成 SrVO2H、Sr2VO3H 和 Sr3V2O5H2。这些新相包含由顶点连接的 V(3+)O4 正方形链组成的片层或链,与 SrH 层/链堆叠在一起,使得 n=∞ 成员 SrVO2H 可以被认为类似于“无限层”相,例如 Sr(1-x)Ca(x)CuO2(高温超导铜酸盐的母体相),但具有 d(2)电子计数。所有三种氧化物-氢化物相都表现出强烈的反铁磁耦合,其中 SrVO2H 表现出反铁磁有序温度 T(N)>300 K。鉴于它们似乎来自 π 型磁交换,这些强烈的反铁磁耦合令人惊讶。

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