Stabilization Of The CN 3 5- Anion In Recoverable High-pressure Ln 3 O 2 (CN 3 ) (Ln=La, Eu, Gd, Tb, Ho, Yb) Oxoguanidinates
Stabilization Of The CN 3 5- Anion In Recoverable High-pressure Ln 3 O 2 (CN 3 ) (Ln=La, Eu, Gd, Tb, Ho, Yb) Oxoguanidinates
复制标题
可回收高压Ln 3 O 2 (CN 3 ) (Ln=La、Eu、Gd、Tb、Ho、Yb)氧代胍盐中CN 3 5-阴离子的稳定化
DOI：
10.1002/ange.202311516
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发表时间：
2023
影响因子：
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通讯作者：
Aslandukov A
中科院分区：
文献类型：
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作者：
Aslandukov A
在激光加热金刚石砧池中，在高压（25-54GPa）高温（2000-3000K）条件下合成了一系列同构 Ln3O2(CN3)（Ln=La、Eu、Gd、Tb、Ho、Yb）氧代胍盐。这类新型化合物的晶体结构通过同步加速器单晶 X 射线衍射 (SCXRD) 确定，并通过 X 射线吸收近边结构 (XANES) 测量和密度泛函理论 (DFT) 计算得到证实。 Ln3O2(CN3) 固体由迄今为止未知的 CN35−胍酸根阴离子——去质子化胍组成。发现 Ln3O2(CN3) (Ln=La、Eu、Gd、Tb、Ho、Yb) 化合物的晶胞体积和可压缩性的变化是由镧系元素收缩现象决定的。减压实验表明，Ln3O2(CN3) 化合物可恢复至环境条件。 CN35−胍酸根阴离子在环境条件下的稳定性为无机和有机合成化学提供了新的机遇。
A series of isostructural Ln3O2(CN3) (Ln=La, Eu, Gd, Tb, Ho, Yb) oxoguanidinates was synthesized under high‐pressure (25–54 GPa) high‐temperature (2000–3000 K) conditions in laser‐heated diamond anvil cells. The crystal structure of this novel class of compounds was determined via synchrotron single‐crystal X‐ray diffraction (SCXRD) as well as corroborated by X‐ray absorption near edge structure (XANES) measurements and density functional theory (DFT) calculations. The Ln3O2(CN3) solids are composed of the hitherto unknown CN35−guanidinate anion—deprotonated guanidine. Changes in unit cell volumes and compressibility of Ln3O2(CN3) (Ln=La, Eu, Gd, Tb, Ho, Yb) compounds are found to be dictated by the lanthanide contraction phenomenon. Decompression experiments show that Ln3O2(CN3) compounds are recoverable to ambient conditions. The stabilization of the CN35−guanidinate anion at ambient conditions provides new opportunities in inorganic and organic synthetic chemistry.