结晶学
化学
晶体结构
齿合度
范德瓦尔斯力
化学计量学
热分解
价(化学)
X射线晶体学
单晶
方形金字塔分子几何
分子
衍射
物理化学
有机化学
物理
光学
作者
P. Malinowski,Dominik Kurzydłowski,Wojciech Grochala
出处
期刊:Dalton Transactions
[The Royal Society of Chemistry]
日期:2015-01-01
卷期号:44 (45): 19478-19486
被引量:7
摘要
The reaction of AgF2 with P2O3F4 yields a mixed valence Ag(I)/Ag(II) difluorophosphate salt with AgAg(PO2F2)14 stoichiometry - the first Ag(ii)-PO2F2 system known. This highly moisture sensitive brown solid is thermally stable up to 120 °C, which points at further feasible extension of the chemistry of Ag(ii)-PO2F2 systems. The crystal structure shows a very complex bonding pattern, comprising of polymeric Ag(PO2F2)14(4-) anions and two types of Ag(I) cations. One particular Ag(II) site present in the crystal structure of Ag9(PO2F2)14 is the first known example of square pyramidal penta-coordinated Ag(ii) in an oxo-ligand environment. Ag(i)PO2F2 - the product of the thermal decomposition of Ag9(PO2F2)14 - has also been characterized by thermal analysis, IR spectroscopy and X-ray powder diffraction. It has a complicated crystal structure as well, which consists of infinite 1D [Ag(I)O4/2] chains which are linked to more complex 3D structures via OPO bridges. The PO2F2(-) anions bind to cations in both compounds as bidentate oxo-ligands. The terminal F atoms tend to point inside the van der Waals cavities in the crystal structure of both compounds. All important structural details of both title compounds were corroborated by DFT calculations.
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