Sulfone-Functionalized Chichibabin's Hydrocarbons: Stable Diradicaloids with Symmetry Breaking Charge Transfer Contributing to NIR Emission beyond 900 nm

Zhou, Zhibiao1,2,3; Yang, Kun1,2; He, Long1,4; Wang, Wei3; Lai, Weiming1,2; Yang, Yinhua5; Dong, Yueguo6; Xie, Sheng1,2; Yuan, Lin1,2; Zeng, Zebing1,2

2024-02-28

10.1021/jacs.3c13270

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   影响因子和分区

0002-7863

1520-5126

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-C-2 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 (similar to 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.

SCI ; IC ; EI

英语

其他

National Natural Science Foundation of China["52350058","22375059"] ; National Natural Science Foundation of China[RCJC20200714114434015]

Chemistry

Chemistry, Multidisciplinary

WOS:001179620000001

AMER CHEMICAL SOC

Web of Science

1.Hunan Univ, Coll Chem & Chem Engn, State Key Lab Chemo Biosensing & Chemometr, Changsha 410082, Peoples R China
2.Hunan Univ, Shenzhen Res Inst, Shenzhen 518000, Peoples R China
3.Hunan Univ Chinese Med, Innovat Mat Med Res Inst, Sch Pharm, TCM & Ethnomed Innovat & Dev Int Lab, Changsha 410208, Peoples R China
4.Hunan Univ Sci & Technol, Sch Chem & Chem Engn, Key Lab Theoret Organ Chem & Funct Mol, Minist Educ, Xiangtan 411201, Peoples R China
5.Southern Univ Sci & Technol, Core Res Facil, Shenzhen 518055, Guangdong, Peoples R China
6.Tianjin Jiuri New Mat Co Ltd, Tianjin 300384, Peoples R China

Zhou, Zhibiao,Yang, Kun,He, Long,et al. Sulfone-Functionalized Chichibabin's Hydrocarbons: Stable Diradicaloids with Symmetry Breaking Charge Transfer Contributing to NIR Emission beyond 900 nm[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2024,146(10).

Zhou, Zhibiao.,Yang, Kun.,He, Long.,Wang, Wei.,Lai, Weiming.,...&Zeng, Zebing.(2024).Sulfone-Functionalized Chichibabin's Hydrocarbons: Stable Diradicaloids with Symmetry Breaking Charge Transfer Contributing to NIR Emission beyond 900 nm.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,146(10).

Zhou, Zhibiao,et al."Sulfone-Functionalized Chichibabin's Hydrocarbons: Stable Diradicaloids with Symmetry Breaking Charge Transfer Contributing to NIR Emission beyond 900 nm".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 146.10(2024).