Crystal structure of formamidinium-lead-chloride-dimethyl sulfoxide and phase relationship of related crystalline systems
Crystal structure of formamidinium-lead-chloride-dimethyl sulfoxide and phase relationship of related crystalline systems
复制标题
甲脒-氯化铅-二甲亚砜的晶体结构及相关晶系的相关系
DOI：
10.1039/d2ce00889k
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发表时间：
2022
期刊：
影响因子：
3.1
通讯作者：
Ohashi Naoki
中科院分区：
文献类型：
--
作者：
Saito Noriko;Matsushita Yoshitaka;Ohsawa Takeo;Segawa Hiroyo;Ohashi Naoki
在二甲基亚砜（DMSO）（（CH 3）2SO）溶液中，溶解了氯化甲脒（FA）和氯化铅（II），合成了[CH（NH 2）2]Pb（C2 H6 OS）Cl 3晶体。单晶X射线衍射研究表明，[CH（NH 2）2]Pb（C2 H6 OS）Cl 3在113-293 K温度范围内具有单斜（P21/c）对称性。有趣的是，DMSO中的氧原子参与了扭曲的[PbOCl 5]八面体，其通过边缘共享形成[Pb 2 O2 Cl 9]二聚体单元。这些二聚体单元通过角共享形成平行于（100）平面伸长的伪2D锯齿形层。FA+阳离子在结构上是有序的，并在由[Pb 2 O2 Cl 9]二聚体单元包围的空隙处的伪二维锯齿形层之间对齐。使用密度泛函理论方法计算的DMSO溶剂化物的形成焓解释了FAPbCl 3-DMSO溶剂化物的相稳定性。
Single crystals of formamidinium (FA)–lead–chloride–dimethyl sulfoxide (DMSO) solvate, [CH(NH2)2]Pb(C2H6OS)Cl3, were synthesized from a DMSO ((CH3)2SO) solution in which FA–chloride (CH(NH2)2Cl) and lead(II) chloride (PbCl2) were dissolved. Single-crystal X-ray diffraction studies revealed that [CH(NH2)2]Pb(C2H6OS)Cl3 exhibited a monoclinic (P21/c) symmetry in the temperature range of 113–293 K. Interestingly, the oxygen atom of DMSO was involved in the distorted [PbOCl5] octahedra, which form a [Pb2O2Cl9] dimer unit by edge-sharing. These dimer units form a pseudo-2D zigzag layer elongated parallel to the (100) plane via corner sharing. The FA+ cation was structurally ordered and aligned between the pseudo-2D zigzag layers at the voids surrounded by the [Pb2O2Cl9] dimer units. The formation enthalpy of the DMSO solvate calculated using the density functional theory method explains the phase stability of the FAPbCl3–DMSO solvate.