| 大环芳烃菲咯啉的设计、合成及其铜光敏剂光解水制氢性能 | |
| Macrocyclic Arenes Derived Phenanthrolines: Design, Synthesis and Application at Heteroleptic Copper Complexes for Photocatalytic Hydrogen Evolution from Water | |
| 摘要: 设计、合成了一类4，7位为大环芳烃的菲咯啉二齿氮配体，可与铜（Ⅰ）和Xantphos原位配位，获得一系列新型氮磷杂配铜光敏剂CuPS 1~CuPS 6，在均相光解水制氢体系中研究其光敏活性及构效关系。实验结果表明，在菲咯啉4，7位引入芳基有利于提高其光敏活性，1-萘基取代的CuPS 3有最好的制氢活性，光解水制氢转化数（TON）达957。通过理论计算对比分析，1-萘基取代基与菲咯啉母核具有较大的二面角，对铜配合物的激发态有较好的保护作用，因此CuPS 3表现出较高的荧光量子产率（0.036）和较长的激发态寿命（1.36 μs）。 | |
| 关键词: 大环芳烃 菲咯啉 铜光敏剂 光解水 制氢 | |
| 基金项目: | |
| Abstract: A series of macrocyclic arenes derived phenanthrolines have been designed and synthesized, which could form a series of novel heteroleptic copper photosensitizers CuPS 1~CuPS 6 with Xantphos as phosphorus ligands. The photosensitive activity of CuPS 1~CuPS 6 was studied in homogeneous photocatalytic water reduction system for hydrogen production. The research results showed that 1-naphthyl was the preferred substituent and the turnover number (TON) of CuPS 3 for hydrogen production was up to 957. Through theoretical calculation and comparative analysis, a larger dihedral angle of the 1-naphthyl substituent and the phenanthroline nucleus has a better steric effect to protect the excited state of the copper complex. Thus, CuPS 3 displayed a higher fluorescence quantum yield (0.036) and a longer excited state lifetime (1.36 μs). | |
| Keywords: macrocyclic arene phenanthroline copper photosensitizer photocatalytic water splitting hydrogen evolution | |
| 投稿时间：2021-02-09 修订日期：2021-07-14 | |
| 摘要点击次数: 944 | |
| 全文下载次数: 447 | |
| 许萌,俞晓聪,刘雪粉,陈浩,范金轩,王天琦,吴庆安,罗书平.大环芳烃菲咯啉的设计、合成及其铜光敏剂光解水制氢性能[J].无机化学学报,2021,37(9):1597-1605. | |
| 查看全文 查看/发表评论 下载PDF阅读器 | |
| Support information: | |
|
| |
|
| |
|
| |