Li Jingpeng, Zhang Meiyu, Li Wenxuan, Li Zhongshu, Zhu Tingshun, Yang Zhenyu
MOE Laboratory of Bioinorganic and Synthetic Chemistry, Lehn Institute of Functional Materials, School of Chemistry, IGCME, Sun Yat-sen University, Guangzhou, Guangdong, China.
Nat Commun. 2025 Jul 19;16(1):6664. doi: 10.1038/s41467-025-62002-7.
Silicon is a cornerstone material in electronics and photovoltaics due to its abundance, tunable semiconducting properties, and chemical versatility. Direct anchoring of thiophenes, with their highly delocalized aromatic backbones, onto silicon surfaces offers a promising route to tailor charge carrier migration properties. However, current methods for anchoring thiophenes commonly rely on pre-activation of precursors or transition-metal catalysts. Here, we introduce a catalyst-free radical strategy for direct linkage of thiophenes with Si atoms on organosilanes and silicon surfaces. This method leverages thermally induced homolytic cleavage of Si-H bonds to generate silicon radicals, which undergo efficient hydrosilylation with thiophene rings, forming Si-C linkages and releasing H. We demonstrate the successful application of this approach on silicon surfaces, achieving functionalization with thiophenes that enhance charge carrier mobilities in silicon nanocrystals significantly higher than previously reported alkyl-functionalized SiNCs, indicating the significant potential of catalyst-free dehydrocoupling for advancing silicon-based materials in optoelectronic applications.
硅因其储量丰富、半导体性能可调以及化学多功能性，成为电子学和光伏领域的基石材料。噻吩具有高度离域的芳香骨架，将其直接锚定在硅表面为定制电荷载流子迁移特性提供了一条有前景的途径。然而，目前锚定噻吩的方法通常依赖于前体的预活化或过渡金属催化剂。在此，我们介绍一种无催化剂的自由基策略，用于在有机硅烷和硅表面将噻吩与硅原子直接连接。该方法利用热诱导的Si-H键均裂产生硅自由基，硅自由基与噻吩环进行高效的硅氢加成反应，形成Si-C键并释放出H。我们展示了该方法在硅表面的成功应用，实现了用噻吩进行功能化，显著提高了硅纳米晶体中的电荷载流子迁移率，比之前报道的烷基功能化硅纳米晶体高得多，这表明无催化剂脱氢偶联在推进硅基材料用于光电子应用方面具有巨大潜力。
