Wang Sisi, Lu Hua, Wu Yanping, Xiao Xuqiong, Li Zhifang, Kira Mitsuo, Shen Zhen
Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University, Hangzhou, 310012, China.
State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing, 210093, China.
Chem Asian J. 2017 Mar 2;12(5):561-567. doi: 10.1002/asia.201601637. Epub 2017 Jan 27.
We describe herein the first synthesis of silyl- and disilanyl-BODIPYs through transition-metal-catalyzed dehalosilylation of iodo-BODIPYs using a Pd(P(tBu) ) /Et N/toluene system. Various mono- and bis-silyl-BODIPYs, mono- and bis-disilanyl-BODIPYs and bis-BODIPYs linked by silylene and SiOSi groups were synthesized by using this straightforward method. Silyl- and disilanyl-substitution significantly modifies the spectroscopic properties of the BODIPY, in which the fluorescence quantum yields of the silyl-BODIPYs are remarkably increased, whereas the emission spectra of disilanyl-BODIPYs are red-shifted due to effective σ(SiSi)-π(BODIPY) conjugation.
我们在此描述了通过使用 Pd(P(tBu)₃)/Et₃N/甲苯体系对碘代 BODIPY 进行过渡金属催化的脱卤硅基化反应首次合成硅基和二硅烷基 BODIPY。通过这种直接的方法合成了各种单硅基和双硅基 BODIPY、单二硅烷基和双二硅烷基 BODIPY 以及通过硅烯和 SiOSi 基团连接的双 BODIPY。硅基和二硅烷基取代显著改变了 BODIPY 的光谱性质，其中硅基 BODIPY 的荧光量子产率显著提高，而二硅烷基 BODIPY 的发射光谱由于有效的 σ(Si-Si)-π(BODIPY)共轭而发生红移。
