-三键复合物的强过渡金属
Holger Braunschweig1,2, Theresa Dellermann1,2, Rian D Dewhurst1,2
1Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg , Am Hubland, 97074 Würzburg, Germany.
Journal of the American Chemical Society
|February 22, 2017
概括
这项研究报告了使用铜的第一个具有-三重键 (diborynes) 的过渡金属π-复合物. 这些新型的二博林复合物表现出高效的红至近红外光,这是基材料的重大进步.
科学领域:
- 有机金属化学
- 无机化学
- 材料科学
背景情况:
- 过渡金属的π-复合物在催化和材料科学中至关重要.
- -和-碳化合物已被探索,但-多重键的理解较少.
- 最近的进展包括含有 diborynes 的金属离子复合物.
研究的目的:
- 合成和描述与过渡金属铜的第一个-三键复合物 (diborynes).
- 研究这些新奇的Cu-diboryne复合物的结构,电子和光物理特性.
- 将它们的特性与现有的二博林和二博林复合物进行比较.
主要方法:
- 三种不同的Cu-diboryne复合物的合成.
- 使用X射线衍射和NMR光谱 (11B NMR) 的结构特征.
- 光物理研究包括光谱和终身测量.
- 密度函数理论 (DFT) 的计算.
主要成果:
- 分离了三种Cux-π-diboryne化合物 (n=2,3).
- 在11B NMR中观察到B-B和B-C键的延长和显著的上场转移,表明强烈的轨道相互作用.
- 强红至近红外光 (高达58%的量子产量) 从三次激发状态与微秒寿命.
- DFT研究显示了对HOMO/HOMO-1的显著Cu d轨道贡献,导致MLCT特征和高效的系统间交叉.
结论:
- 已经成功合成和描述了第一个Cu (I) π复合物.
- 这些复合体具有独特的电子结构,具有大量的金属-连接体轨道混合.
- 这种复合物表现出高效的光,为新的光电子材料开辟了道路.
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