氧化作为在WO3/素/NaCN系统中合成具有不同核度的复合物的通用来源
Spartak S Yarovoy1, Irina V Mirzaeva1, Taisiya S Sukhikh1
1Nikolaev Institute of Inorganic Chemistry SB RAS, Acad. Lavrentiev ave. 3, 630090 Novosibirsk, Russian Federation. yss@niic.nsc.ru.
Dalton transactions (Cambridge, England : 2003)
|May 6, 2025
概括
三氧化物与化和石化 (硫,,) 反应,形成各种化和石化复合物. 合成温度和时间控制单核,三核和四核集群的形成.
科学领域:
- 无机化学 无机化学 有机化学
- 材料科学 材料科学 材料科学
- 协调化学 协调化学
背景情况:
- 三氧化物 (WO3) 作为合成基于的协调化合物的前体.
- 化物和化联体提供了与的多种协调可能性.
- 了解复杂化学系统中的相位形成对于有针对性的合成至关重要.
研究的目的:
- 在250-700°C的温度范围内研究系统6WO3 + 8Q + 32NaCN (Q = S,Se,Te) 中的相位形成.
- 为了识别可溶的青酸和青酸复合物形成.
- 确定这些复合物的存在温度极限,以及合成时间对产品成分的影响.
主要方法:
- 复合物的单步合成.
- 可变温度研究 (250-700°C).
- 光谱表征:13C,77Se和183W的NMR光谱学. 这是一个很好的方法.
- 计算分析:密度函数理论 (DFT) 的计算.
- 结构确定:单晶X射线衍射分析.
主要成果:
- 观察到一个取决于温度的转变序列:单核复合物 → 集群复合物 → 二基因化物.
- 确定的特定复合体包括[W(CN) ]4-,[WS4]2-,[WS3O]2-,三核[{W3Q4}(CN) ]9-5- (Q=S,Se),[{W3S3O}(CN) 9-5-,以及四核[{W4Q4}(CN) 12-6- (Q=S,Se,Te).
- 确定了四种特定盐的晶体结构.
- 具有不同核心组成的三核复合物的比率 (异质复合与同质复合) 受合成时间在300°C的影响.
结论:
- 合成条件 (温度和时间) 显著影响形成的酸和酸复合物的类型和组成.
- 核磁共振光谱和DFT计算对于表征这些复杂的物种是有效的.
- 该研究提供了有关合成过程中集群核的动态转换的见解.
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