Di Linting, Yang Jie, Tang Weiguo, Gai Lizhi, Zhou Zhikuan, Lu Hua
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, and Key Laboratory of Organosilicon Material Technology of Zhejiang Province, Hangzhou Normal University, No. 2318, Yuhangtang Road, Hangzhou 311121, P. R. China.
State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093, P. R. China.
J Org Chem. 2021 Jan 1;86(1):601-608. doi: 10.1021/acs.joc.0c02274. Epub 2020 Dec 2.
The fusion of sufficient-electron heterocycle rings into the[]/[]-position of the BODIPY core would result in a large redshift wavelength, thus achieving red or near infrared emission. In this paper, we described the synthesis of nonsymmetric benzo[]fused and thiophene/thieno[3,2-]thiophene[]fused BODIPY derivatives while containing a reactive site, and then, were developed by nucleophilic substitution reactions of with various nucleophilic agents in high yields. X-ray crystallographic analysis of revealed that the core structure adopted a planar geometry and π-π interactions were observed in the packing structure. BODIPYs and displayed a hypochromic shift in the absorption and bathochromic shift in the emission with increasing solvent polarity because of the formation of resonance structures resulting from the change of the C-N distance, which was rationalized by density functional theory (DFT)/time-dependent-DFT calculations.
将足够电子的杂环环融合到BODIPY核的[]/[]位置会导致较大的红移波长，从而实现红色或近红外发射。在本文中，我们描述了不对称苯并[]稠合和噻吩/噻吩并[3,2-]噻吩[]稠合的BODIPY衍生物的合成，同时含有一个反应位点，然后通过与各种亲核试剂的亲核取代反应以高产率得到这些衍生物。对[具体化合物]的X射线晶体学分析表明，其核心结构采用平面几何形状，并且在堆积结构中观察到π-π相互作用。由于C-N距离变化导致共振结构的形成，BODIPY [具体化合物]和[具体化合物]随着溶剂极性的增加在吸收上呈现减色位移，在发射上呈现红移，这通过密度泛函理论（DFT）/含时密度泛函理论计算得到了合理的解释。
