Structural Features in Some Layered Hybrid Copper Chloride Perovskites: ACuCl4 or A2CuCl4
Structural Features in Some Layered Hybrid Copper Chloride Perovskites: ACuCl4 or A2CuCl4
复制标题
DOI：
10.1021/acs.inorgchem.1c00705
复制
发表时间：
2021-07-09
影响因子：
4.6
通讯作者：
Lightfoot, Philip
中科院分区：
文献类型：
--
作者：
Han, Ceng;Bradford, Alasdair J.;Lightfoot, Philip
我们提出了三种新的混合氯化铜（II）层状钙钛矿的一般组成ACuCl（4）或A（2）CuCl（4），表现出三种不同的结构类型。（m-PdH 2）CuCl 4（m-PdH 22 + =质子化的间苯二胺）采用Dion-Jacobson（DJ）状层状钙钛矿结构类型，并且在加热时表现出非常大的轴向热收缩效应，如通过变温同步辐射X射线粉末衍射（SXRD）所揭示的。这可以归因于通过m-PdH 22+部分的轻微重新定位的层间嵌段的收缩。（3-AbaH）（2）CuCl 4（3-AbaH（+）=质子化的3-氨基苯甲酸）和（4-AbaH）（2）CuCl 4（4-AbaH（+）=质子化的4-氨基苯甲酸）具有与Ruddlesden-Popper（RP）层状钙钛矿A（2）BX（4）相同的通式，但采用不同的结构。（4-AbaH）（2）CuCl_4采用近交错结构类型，而（3-AbaH）（2）CuCl_4采用近重叠结构类型，其类似于DJ而不是RP家族。（3-AbaH）（2）CuCl_4也表现出[CuCl_4]（无穷）层的静态无序。每个的晶体结构的模板分子物种的不同性质的方面进行了讨论，这些相比相关的层状钙钛矿。初步磁性测量报告，表明占主导地位的铁磁相互作用。
We present three new hybrid copper(II) chloride layered perovskites of generic composition ACuCl(4) or A(2)CuCl(4), which exhibit three distinct structure types. (m-PdH2)CuCl4 (m-PdH22+ = protonated m-phenylenediamine) adopts a Dion-Jacobson (DJ)-like layered perovskite structure type and exhibits a very large axial thermal contraction effect upon heating, as revealed via variable-temperature synchrotron X-ray powder diffraction (SXRD). This can be attributed to the contraction of an interlayer block, via a slight repositioning of the m-PdH22+ moiety. (3-AbaH)(2)CuCl4 (3-AbaH(+) = protonated 3-aminobenzoic acid) and (4-AbaH)(2)CuCl4 (4-AbaH(+) = protonated 4-aminobenzoic acid) possess the same generic formula as Ruddlesden-Popper (RP) layered perovskites, A(2)BX(4), but adopt different structures. (4-AbaH)(2)CuCl4 adopts a near-staggered structure type, whereas (3-AbaH)(2)CuCl4 adopts a near-eclipsed structure type, which resembles the DJ rather than the RP family. (3-AbaH)(2)CuCl4 also displays static disorder of the [CuCl4](infinity) layers. The crystal structures of each are discussed in terms of the differing nature of the templating molecular species, and these are compared to related layered perovskites. Preliminary magnetic measurements are reported, suggesting dominant ferromagnetic interactions.