Thiophene-Derived Boron-Containing Dioxoborocyclic Blue-Luminescent Radicals

doi:10.6023/

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (2): 664-669.DOI: 10.6023/ Previous Articles Next Articles

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含噻吩基团的二氧杂硼环蓝光自由基

鹿馨元^a^,^b^,^†, 董学^c^,^†^,^*(), 孙全春^b, 王滔^b, 雷川虎^a^,^*(), 王新平^b^,^*()

^a 上海大学理学院化学系超分子化学与催化研究中心上海 200444
^b 中国科学院上海有机化学研究所金属有机化学国家重点实验室上海 200032
^c 山东海化集团潍坊 262737

收稿日期:2025-08-11 修回日期:2025-09-19 发布日期:2025-10-09
通讯作者: 董学, 雷川虎, 王新平
作者简介:
^† 共同第一作者
基金资助:
国家自然科学基金(22231005); 中国科学院战略重点研究计划(XDB0610000)

Thiophene-Derived Boron-Containing Dioxoborocyclic Blue-Luminescent Radicals

Xinyuan Lu^a^,^b, Xue Dong^c^,^*(), Quanchun Sun^b, Tao Wang^b, Chuanhu Lei^a^,^*(), Xinping Wang^b^,^*()

^a Center for Supramolecular Chemistry and Catalysis, Department of Chemistry, College of Science, Shanghai University, Shanghai 200444
^b State Key laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
^c Shandong Haihua Co., Ltd., Weifang 262737

Received:2025-08-11 Revised:2025-09-19 Published:2025-10-09
Contact: Xue Dong, Chuanhu Lei, Xinping Wang
About author:
^† These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22231005); Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0610000)

Abstract

Luminescent radicals have attracted extensive attention due to the unique emission properties from the doublet spin state. However, luminescent radicals are predominantly chloroarylmethyl radicals that emit light in the red and near-infrared spectral regions, and the blue emitting radicals remain scarcely reported. Herein, two novel boron-containing dioxoborocyclic blue-luminescent radicals were designed and synthesized by combining dioxoborocyclic radicals with thiophene units. They were characterized by single-crystal X-ray diffraction, UV-Vis spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, and fluorescence spectroscopy in conjunction with theoretical calculations. Theoretical calculations demonstrate that both radicals 3a and 3b emit blue light from the anti-Kasha emission attributed to the effective suppression of IC pathways. Our work offers definitive proof that the boron-containing radical system functions as a highly efficient platform for expanding the diversity of short-wavelength emissive radicals.

Key words: borocyclic radical, blue-luminescent radicals, thiophene-derived

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Xinyuan Lu, Xue Dong, Quanchun Sun, Tao Wang, Chuanhu Lei, Xinping Wang. Thiophene-Derived Boron-Containing Dioxoborocyclic Blue-Luminescent Radicals[J]. Chinese Journal of Organic Chemistry, 2026, 46(2): 664-669.

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Fig. & Tab. 5

Scheme 1. Synthesis of radicals 3a and 3b

Figure 1. Thermal ellipsoid drawings (at 50% probability) with selected bond lengths of molecules and crystal packings of 3a (a, c) and 3b (b, d) Hydrogen atoms and solvent molecules are omitted for clarity. C: gray, F: green, O: red, B: yellow, S: orange. Selected bond lengths (Å): 3a: C(1)—O(1) 1.313(2), C(2)—O(2) 1.315(2), C(1)—C(2) 1.428(3), B—O(1) 1.530(3), B—O(2) 1.521(3); 3b: C(1)—O(1) 1.306(4), C(2)— O(2) 1.318(4), C(1)—C(2) 1.437(5), B—O(1) 1.533(5), B—O(2) 1.508(5).

Figure 2. EPR spectra of 3a (a) and 3b (b) in toluene at room temperature with simulation, and spin densities of 3a (c) and 3b (d) calculated at the UB3LYP/6-311G(d) level

Figure 3. (a) Fluorescence spectra excited at 398 nm of 3a and 338 nm of 3b in DCM at room temperature; (b) Fluorescence decay of 3a and 3b following excitation at 375 nm for 3a and 3b

Figure 4. Energy levels and wavefunctions for the ground state frontier molecular orbitals of 3a (a) and 3b (b), calculated at UB3LYP/6-31G(d) level of theory

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含噻吩基团的二氧杂硼环蓝光自由基

Thiophene-Derived Boron-Containing Dioxoborocyclic Blue-Luminescent Radicals

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