含有化物八个电子的Pt/Ag超原子:结构,结合和多NMR研究
Tzu-Hao Chiu1, Jian-Hong Liao1, Franck Gam2
1Department of Chemistry, National Dong Hwa University, Hualien 974301, Taiwan (Republic of China).
Journal of the American Chemical Society
|June 2, 2022
概括
这项研究首次使用中子衍射精确地定位化物在/银纳米集群中. 化物是这些新型化物合的高贵金属纳米集团中超原子核的关键部分.
科学领域:
- 无机化学
- 材料科学
- 纳米技术
- 超原子化学
背景情况:
- 有趣的是化物合的贵金属纳米集群,化物被认为是超原子核心的一部分.
- 这些纳米集群中封装的化物的确切位置的实验证据一直缺乏.
- 了解超原子纳米集群的结构属性关系对于它们的应用至关重要.
研究的目的:
- 通过实验确定化物在/银合金纳米集群中的确切位置.
- 描述化物合/银纳米集群的固态和溶液结构.
- 通过计算方法研究超原子核的电子结构和结合.
主要方法:
- 化物合金纳米集群的合成: [PtHAg19(dtp/desp) 12.
- 单晶X射线衍射以确定固态结构.
- 通过中子衍射精确定位四坐标化物.
- 核磁共振 (NMR) 光谱 (H,Pt,多NMR) 用于研究溶液结构和同位素.
- 密度函数理论 (DFT) 计算以分析电子结构和同位素能量.
主要成果:
- 第一次通过中子衍射确定一个四坐标的精确位置,位于中央PtH单元内.
- X射线结构揭示了由银原子和二基酸盐封装的[PtH@Ag12]核心,在固态中呈现不同的对称性 (C1和C3).
- 核磁共振研究表明C1和C3异构体在溶液中共存,得到了DFT计算的支持,显示了相似的能量.
- DFT计算证实[PtH@Ag12]5+核是一个封闭的八个电子超原子核,化物对其电子数量有显著的贡献.
结论:
- 这项研究提供了第一个实验证据,证明化物位于高贵金属纳米集团的超原子核中.
- 结果突出了化物合/银纳米集群的结构多样性和异构复杂性,无论是固态还是溶液状态.
- 这些发现有助于我们更好地理解超原子化学和封装化物在稳定这些独特的纳米结构中的作用.
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