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A re‐interpretation of the structure of the silver borate, Ag16B4O10, in the light of the extended Zintl–Klemm concept
Acta Crystallographica Section B ( IF 2.684 ) Pub Date : 2020-09-23 , DOI: 10.1107/s2052520620010513
Angel Vegas , H. Donald Brooke Jenkins

The borate Ag16B4O10 was synthesized at high temperature and at elevated oxygen pressures [Kovalevskiy et al. (2020). Chem. Sci.11, 962–969]. Its structure consists of [B4O10]8− polyanions (isostructural to P4O10) embedded in an Ag matrix. According to the standard valences Ag+, B3+ and O2−, the formula has an excess of eight e which the above authors proposed were located, pairwise, in four Ag4 tetrahedra within the silver substructure. That conclusion was based on the semiconducting and diamagnetic properties, as well as the very small `attractors' of the Electron Localization Function (ELF) found at the centre of these Ag4 tetrahedra. However, a large overlap of the projected density of states (DOS) of silver and oxygen indicated possible dispersion interactions between both atomic species. In this article, an alternative description is proposed based on the extended Zintl–Klemm concept. The anion [B4O10]8− can be formulated as Ψ‐[N4O10] P4O10, if it is assumed that the eight e are transferred to the four B atoms, so converting them into Ψ‐N, this then makes sense of its similarity with P4O10, [N4(CH2)6], adamantane and tetraisopropyladamantane. When the Ag atoms connect to the O atoms, they arrange as the H atoms do in hexamethylenetetramine (HMTA). If the two lone pairs of each of the bridging O atoms in Ψ‐[N4O10] are equated to the C—H bonds in HMTA, then, this same equivalence exists between the C—H bonds and the O—Ag bonds in the compound Ag16B4O10. The 24 Ag atoms surrounding each [B4O10]8− group prolong the sphalerite structure of the borate anion by means of Ag—O bonds which also fit the sphalerite structure formed of AgO. The eight excess electrons might then be distributed between the Ag and the O atoms, so making sense of the mixing of the Ag and O states. The Ag atoms bonded to the O atoms of the [B4O10]8− groups form a coat that interconnects the borate anions through Ag—O bonds. To establish the validity of this new proposal, the study needs to be extended to the compound Ag3B5O9.

中文翻译:

根据扩展的Zintl–Klemm概念重新解释了硼酸银Ag16B4O10的结构

硼酸盐Ag 16 B 4 O 10是在高温和升高的氧气压力下合成的[Kovalevskiy等。(2020)。化学 科学 11,962-969]。它的结构由嵌入在银基质中的[B 4 O 10 ] 8−聚阴离子(与P 4 O 10等价)组成。根据标准化合价的Ag +,B 3+和O 2-,公式具有8和E的过量-其中提出的上述作者均位于,成对,在4的Ag 4银亚结构内的四面体。该结论是基于半导体和抗磁特性,以及在这些Ag 4四面体的中心发现的非常小的电子定位函数(ELF)的“吸引子” 。但是,银和氧的预计态密度(DOS)的较大重叠表明两种原子物种之间可能存在色散相互作用。在本文中,基于扩展的Zintl–Klemm概念提出了另一种描述。阴离子[B 4 ø 10 ] 8-可以配制为Ψ-[N 4 ø 10 ] p 4 ö 10,如果假设,该8个E -被转移到四个B原子上,因此将它们转换为Ψ-N,这便使其与P 4 O 10,[N 4(CH 26 ],金刚烷和四异丙基金刚烷相似。当Ag原子连接到O原子时,它们的排列方式与H原子在六亚甲基四胺(HMTA)中的排列方式相同。如果Ψ-[N 4 O 10 ]中每个桥接O原子的两个孤对都等同于HMTA中的CH键,则在CH键与O-Ag键之间存在相同的等价关系在化合物Ag 16 B 4 O 10中。每个[B 4 O 10 ]周围的24个Ag原子8-基团通过Ag-O键延长了硼酸根阴离子的闪锌矿结构,这也适合由AgO形成的闪锌矿结构。然后,八个多余的电子可能会分布在Ag和O原子之间,因此可以理解Ag和O态的混合。与[B 4 O 10 ] 8-基团的O原子键合的Ag原子形成一层涂层,该涂层通过Ag-O键使硼酸根阴离子相互连接。为了确定该新建议的有效性,需要将研究范围扩展到化合物Ag 3 B 5 O 9
更新日期:2020-10-07
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