Yuan Jennifer, Xu Zhen, Wolf Michael O
Department of Chemistry, University of British Columbia 2036 Main Mall Vancouver British Columbia V6T 1Z1 Canada
Chem Sci. 2022 Apr 28;13(19):5447-5464. doi: 10.1039/d2sc01128j. eCollection 2022 May 18.
The use of a heteroatom, such as sulfur, as a linker or bridge, in π-conjugated materials has advantages over purely carbon-based ones due to the accessibility of higher oxidation states as a result of hypervalence. Materials containing a sulfide bridge (S) can be systemically oxidized into sulfoxides (SO) and sulfones (SO), each of which can then influence how a material interacts with light, playing a large role in dictating the photophysical and sometimes photochemical properties. In this perspective, we summarize the progress that our group and others have made, showing how oxidation of a sulfur bridge in symmetric bichromophoric dimers and in diimine ligands can influence the excited state behavior in organic π-conjugated materials and metal complexes.
在π共轭材料中使用杂原子（如硫）作为连接基或桥连基团，由于超价态导致的更高氧化态的可及性，相比于纯碳基材料具有优势。含有硫桥（S）的材料可以被系统地氧化为亚砜（SO）和砜（SO₂），每一种氧化产物随后都可以影响材料与光的相互作用方式，在决定光物理性质甚至光化学性质方面发挥重要作用。从这个角度出发，我们总结了我们小组以及其他研究团队所取得的进展，展示了对称双发色团二聚体和二亚胺配体中硫桥的氧化如何影响有机π共轭材料和金属配合物的激发态行为。
