在带红光的轴顶Rh2(II,II) Paddlewheel复合体中以基为中心的光催化生产
Matthew T Fortunato1, Curtis E Moore1, Claudia Turro1
1Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43214, United States.
Journal of the American Chemical Society
|December 6, 2023
概括
合成了具有bpnp连接体的新复合物. 复合物4展示了以配体为中心的光催化H2产生,这是这种反应的首次.
科学领域:
- 协调化学
- 光催化
- 材料科学
背景情况:
- 二极体以其独特的电子结构和催化潜力而闻名.
- 连接体设计对于调整金属复合物的特性和反应性至关重要.
- 了解金属配体相互作用是开发高效光催化剂的关键.
研究的目的:
- 合成和描述一系列具有不同轴联体的新型 (II,II) 复合物.
- 研究这些复合物的光物理性质和电化学行为.
- 探索它们在光催化生产中的潜力.
主要方法:
- 合成cis-[Rh2{DTolF) 2{bpnp) {L) ]2+复合物 (L=pdz,cinn,bncn).
- 电化学分析 (循环电压测量) 来确定还原潜力.
- 紫外线-Vis吸收光谱用于研究电子转换.
- 使用可见光照射在牺牲减光剂和酸的存在下进行光催化实验.
主要成果:
- 合成的复合物呈现出明显的金属/配体对配体电荷转移 (ML-LCT) 波段.
- 复合物4具有[c] (bncn) 连接体,显示出用于H2生成的光催化活性.
- 在特定条件下,使用复合4实现了H2生产,营业额为16.
- 该bpnp连接体的轴性封闭阻止了Rh-H化物形成,局部化了bncn连接体上的反应.
结论:
- 这项研究提出了具有可调节光物理性质的新型 (II,II) 复合物.
- 综合体4中的[c]林连接体被确定为光催化H2生产的活性位点.
- 这项工作展示了双金属系统中以为中心的H2生产的第一个例子.
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