Perovzalates: a family of perovskite-related oxalates.
Perovzalates: a family of perovskite-related oxalates.
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DOI：
10.1039/c9dt03149a
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发表时间：
2019-10
影响因子：
4
通讯作者：
Rebecca Clulow;Alasdair J. Bradford;Stephen L. Lee;P. Lightfoot
中科院分区：
文献类型：
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作者：
Rebecca Clulow;Alasdair J. Bradford;Stephen L. Lee;P. Lightfoot
本文报道了一族钙钛矿-草酸盐杂化化合物，其总组成为AlLi3MII(C2O4)3(A=K+，Rb+，Cs+；M=Fe2+，Co2+，Ni2+)。所有8个新化合物都是同结构的，如先前报道的NH4Li3Fe(C2O4)3和KLi3Fe(C2O4)3，结晶在菱面体空间群R3[结合马克龙]c中，∼为11.3-11.6？，c∼为14.8-15.2？与甲酸盐等杂化钙钛矿不同，这些化合物可以被认为是与无机(氧化物)钙钛矿更接近的结构亲缘关系，因为它们包含通过(草酸基)桥氧原子直接连接八面体位置的键。因此，值得注意的是，与Cs+一样大的单原子阳离子可以被结合到这种结构类型的类钙钛矿型A位中，这在传统的ABO_3钙钛矿中是不可行的；事实上，根据键价分析，CsLi3Ni(C_2O_4)_3在氧化物环境中似乎表现出‘最紧密结合的’12位Cs+离子。
A family of hybrid Perovskite-oxalates ("Perovzalates") of general composition AILi3MII(C2O4)3 (A = K+, Rb+, Cs+; M = Fe2+, Co2+, Ni2+) are presented. All eight new compounds are isostructural with the previously reported examples NH4Li3Fe(C2O4)3 and KLi3Fe(C2O4)3, crystallising in the rhombohedral space group R3[combining macron]c, with a ∼11.3-11.6 Å, c ∼14.8-15.2 Å. In contrast to other families of "hybrid perovskites" such as the formates, these compounds can be regarded as closer structural relatives to inorganic (oxide) perovskites, in the sense that they contain direct linkages of the octahedral sites via bridging oxygen atoms (of the oxalate groups). It is of note, therefore, that monoatomic cations as large as Cs+ can be incorporated into the perovskite-like A sites of this structure type, which is not feasible in traditional ABO3 perovskites; indeed CsLi3Ni(C2O4)3 appears to exhibit the 'mostly tightly bound' 12-coordinate Cs+ ion in an oxide environment, according to a bond valence analysis.