具有封闭电子外的金属化物集群和和素的电子特性
Vikas Chauhan1, Arthur C Reber1, Shiv N Khanna1
1Department of Physics, Virginia Commonwealth University , Richmond, Virginia, United States.
Journal of the American Chemical Society
|January 14, 2017
概括
在 Telluride 集群中的联体交换将电子捐赠者转化为受体. 这项研究表明Co6Te8(PEt3) 6具有较低的电离能,而Co6Te8(CO) 6具有类似素的电子受体特性,两者都有稳定的电子外.
科学领域:
- 无机化学
- 材料科学
- 计算化学
背景情况:
- 具有充满电子外和较大的最高占成分子轨道 (HOMO) - 最低未占用分子轨道 (LUMO) 间隙的集群是稳定的.
- 调整集群电子属性 (电离能,电子亲和力) 通常涉及改变价值电子数量.
研究的目的:
- 证明连接物交换是一种将金属集群的电子角色从捐赠者转换为接受者的方法.
- 研究Co6Te8的电子属性
主要方法:
- 用不同的 (PEt3) 和碳 (CO) 配体合成和表征-化物.
- 对电离能和电子亲和力的实验性确定.
- 电子结构分析,包括HOMO-LUMO间隙.
主要成果:
- Co6Te8(PEt3) 6具有一个封闭的电子外,电离能低 (4.74 eV),HOMO-LUMO间隙为1.24 eV.
- 在Co6Te8 ((PEt3) m ((CO) n中,通过CO联体连续替换PEt3,导致Co6Te8 ((CO) 6产生,它表现为具有高电子亲和度和1.39 eV的HOMO-LUMO间隙的类似素的电子受体.
- 具有偶数连体的集群在金属核心周围采用对称的连体安排.
结论:
- 交换提供了一个可行的策略来调节金属集群的电子功能,而不会改变其核心结构或价值电子数量.
- 这些发现为设计基于金属集群的电子捐赠和接受材料提供了新的可能性.
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