化学
砜
电荷(物理)
对称性破坏
对称(几何)
传输(计算)
聚集诱导发射
光化学
计算化学
高分子化学
光学
荧光
量子力学
物理
几何学
数学
并行计算
计算机科学
作者
Zhengqing Zhou,Kun Yang,Long He,Wei Wang,Weiming Lai,Yinhua Yang,Yunhui Dong,Sheng Xie,Lin Yuan,Zebing Zeng
摘要
While monoradical emitters have emerged as a new route toward efficient organic light-emitting diodes, the luminescence property of organic diradicaloids is still scarcely explored. Herein, by devising a novel radical–radical coupling-based synthetic approach, we report a new class of sulfone-functionalized Chichibabin’s hydrocarbon derivatives, SD-1–3, featuring varied substituent patterns and moderate to high diradical characters of 0.44–0.70, as highly stable diradicaloids with rarely seen NIR emission beyond 900 nm. Via comprehensive experimental and theoretical investigations, we reveal that the optoelectronic and magnetic properties of these materials are significantly tuned by the variations of substitutions (H/CF3/OMe) on the molecular skeletons. More importantly, quantum chemical computations indicate that the embedding of sulfone groups has contributed to a breaking of their quasi-C2 symmetry of these diradicaloid molecules and results in an excited-state charge transfer character. Therefore, a remarkably deep NIR emissive wavelength of up to 998 nm, together with a large Stokes shift (∼386 nm), is achieved for the CF3-based SD-2 molecule in tetrahydrofuran. To the best of our knowledge, such a luminescent wavelength of SD-2 has represented the longest wavelengths among the currently reported organic fluorescent radicals. Overall, our work not only establishes a new synthetic approach toward stable Chichibabin’s hydrocarbons but also paves the way for designing NIR emissive open-shell materials with both fundamental understanding and feasible control of their luminescent properties.
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