聚集诱导发光光催化剂用于快速且耐氧的自由基光聚合

doi:10.6023/cjoc202605006

有机化学 ›› 2026, Vol. 46 ›› Issue (9): 3587-3593.DOI: 10.6023/cjoc202605006 上一篇下一篇

研究论文

聚集诱导发光光催化剂用于快速且耐氧的自由基光聚合

陈怡萱^a, 赵征^a^,^b^,^*()

^a 香港中文大学(深圳)理工学院广东省聚集体科学基础研究卓越中心广东深圳 518172
^b 香港中文大学(深圳)理工学院附属第二医院聚集诱导发光临床转化研究中心广东深圳 518172

收稿日期:2026-05-07 修回日期:2026-07-06 发布日期:2026-08-21
基金资助:
国家重点研发计划(2023YFB3810001); 国家自然科学基金(52333007); 国家自然科学基金(52273197); 国家自然科学基金重大项目(22595400); 国家自然科学基金重大项目(22595401); 深圳市科技创新委员会(KQTD20210811090142053); 深圳市科技创新委员会(JCYJ20230807114213027); 及广东省聚集科学基础研究中心资助项目.

Aggregation-Induced Emission Photocatalysts for Fast and Oxygen-Tolerant Radical Photopolymerization

Yixuan Chen^a, Zheng Zhao^a^,^b^,^*()

^a Guangdong Basic Research Center of Excellence for Aggregate Science, School of Science and Engineering, The Chinese University of Hong Kong (Shenzhen), Shenzhen, Guangdong 518172
^b Clinical Translational Research Center of Aggregation-Induced Emission, The Second Affiliated Hospital, School of Science and Engineering, The Chinese University of Hong Kong (Shenzhen), Shenzhen, Guangdong 518172

Received:2026-05-07 Revised:2026-07-06 Published:2026-08-21
Contact:
^* E-mail: zhaozheng@cuhk.edu.cn
About author:
Dedicated to the 100th anniversary of the birth of Professor Xikui Jiang.
Supported by:
National Key Research and Development Program of China(2023YFB3810001); National Natural Science Foundation of China(52333007); National Natural Science Foundation of China(52273197); Major Project of the National Natural Science Foundation of China(22595400); Major Project of the National Natural Science Foundation of China(22595401); Science Technology Innovation Commission of Shenzhen Municipality(KQTD20210811090142053); Science Technology Innovation Commission of Shenzhen Municipality(JCYJ20230807114213027); Guangdong Basic Research Center of Excellence for Aggregate Science.

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摘要/Abstract

光聚合反应相较于传统的热引发聚合具有显著优势, 如更好的时间可控性及更快的反应动力学. 然而, 传统自由基光固化体系仍面临氧阻聚与光引发剂端基残留的问题. 开发了两个基于苯并噻二唑衍生物的新型光催化剂二苯并[5',6':7',8'][1,4]二氧代辛[2',3':4,5]苯并[1,2-c][1,2,5]噻二唑(PBTH)和二萘并[2'',1'':5',6';1''',2''':7',8'][1,4]二氧代苯并[2',3':4,5]并[1,2-c][1,2,5]噻二唑(BBTH). 通过引入给体-受体(D-A)结构, 光吸收能力和分子内电荷转移(ICT)能力得到提升, 从而增强了光催化性能. 机理研究表明, 激发态光催化剂从N,N,N',N'-四甲基乙二胺(TMEDA)攫取电子生成自由基阴离子和胺烷基自由基, 进而引发丙烯酸酯单体的聚合. 催化剂在聚合前后结构保持不变, 且不通过共价键连接于聚合物链末端. PBTH在质量分数为0.37%的极低负载量下, 于常氧条件下数分钟内, 即可实现近乎完全转化, 并被成功用于“AIE”图案的光刻加工.

关键词: 光催化, 聚集诱导发光(AIE), 紫外光聚合

Photopolymerization offers significant advantages over traditional thermally initiated polymerization, such as better temporal control and faster reaction kinetics. However, conventional systems suffer from oxygen inhibition and initiator end-group residue. Two benzothiadiazole-based photocatalysts, dibenzo[5',6':7',8'][1,4]dioxocino[2',3':4,5]benzo[1,2-c][1,2,5]- thiadiazole (PBTH) and dinaphtho[2'',1'':5',6';1''',2''':7',8'][1,4]dioxocino[2',3':4,5]benzo[1,2-c][1,2,5]thiadiazole (BBTH), were developed. By introducing donor-acceptor (D-A) structures, light absorption and intramolecular charge transfer (ICT) capability are promoted, thereby enhancing the photocatalytic performance. Mechanistic studies reveal that the photoexcited photocatalysis (PC) abstracts an electron from N,N,N',N'-tetramethylethylenediamine (TMEDA), generating a radical anion and an amino- alkyl radical, which subsequently initiates the polymerization of acrylate monomers. The photocatalyst remains intact and is not covalently incorporated into the polymer chain ends. With an extremely low loading of 0.37% (weight percent), PBTH achieved near-complete conversion within minutes under ambient conditions and was successfully employed in the photolithographic fabrication of an “AIE” pattern.

Key words: photocatalysis, aggregation-induce emission (AIE), UV photopolymerization

引用此文

陈怡萱, 赵征. 聚集诱导发光光催化剂用于快速且耐氧的自由基光聚合[J]. 有机化学, 2026, 46(9): 3587-3593.

Yixuan Chen, Zheng Zhao. Aggregation-Induced Emission Photocatalysts for Fast and Oxygen-Tolerant Radical Photopolymerization[J]. Chinese Journal of Organic Chemistry, 2026, 46(9): 3587-3593.

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图/表 9

Scheme 1. Synthesis route of two photocatalysts

Figure 1. (a) UV-vis absorption spectra of three photocatalysts (10 μmol/L in THF); (b) Fluorescence emission spectra of PBTH and BBTH (10 μmol/L in THF); (c) Lifetime decay curves of PBTH and BBTH in solution at 410 nm (10 μmol/L in THF)

Entry	Derivation from standard conditions	Yield/%
1	None	92.4
2	DIPEA instead of TMEDA	62.7
3	TEOA instead of TMEDA	84.7
4	MMA instead of MA	15.5
5	Without base	4.0
6	Without PBTH	0
7	Without light irradiation	0
8	Add TEMPO (1 equiv.)	0
9	FBT instead of PBTH	20.9
10	BBTH instead of PBTH	79.9
11	N₂ atmosphere instead of air	98.3

Table 1. Reaction optimizationaa

Figure 2. Calculated frontier molecular orbitals of the photocatalysts, additives, and monomers at the B3LYP/def2-TZVP level

Entry	PC	Conv./%	M_n/kDa	Đ	n(PC)∶n(MA)∶n(TMEDA)
1	BBTH	79.9	207.8	1.26	1000∶1∶10
2	PBTH	92.4	171.4	1.31	1000∶1∶10
3	PBTH	91.5	96.5	1.37	500∶1∶10
4	PBTH	90.1	212.2	1.28	2000∶1∶10
5	PBTH	65.6	178.3	1.31	4000∶1∶10
6	PBTH	38.3	96.7	1.35	1000∶1∶1
7	PBTH	94.2	98.1	1.36	1000∶1∶40

Table 2. Reaction optimizationa

Entry	Monomer	Conv./%	M_w/kDa	Đ
1	MA	92.2	157.6	1.32
2	BA	90.1	194	1.27
3	HEA	88.3	120.2	1.58
4	NVP	60.1	86.1	1.09
5	VA	10.3	10.5	1.35

Table 3. Expanded polymer monomersa

Figure 3. 1H NMR spectra in CDCl3 of a PBTH/TMEDA/MA mixture (1∶10∶1000, molar ratio) before and after 30 s of UV irradiation (λ=365 nm) and the spectrum of the purified PMA product

Scheme 2. Proposed photocatalytic cycle of polymerization

Figure 4. (a) Plot of monomer conversion vs time for the “on/off” light irradiation cycle experiment; (b) GPC traces of the purified PMA polymers at different time points deviating from the first-order kinetic fit (black dashed line); (c) Photocatalytic polymerization under ambient and open-air conditions (365 nm light irradiation, 150 mW/cm2); (d) GPC traces of photocatalytic polymers obtained under open-air and normoxic conditions; (e) Schematic illustration of a negative photoresist system (PBTH∶TMEDA∶MA∶EGDA=1∶10∶1000∶30, molar ratio) used to generate an “AIE”-shaped pattern (365 nm light irradiation, 150 mW/cm2, 5 min)

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聚集诱导发光光催化剂用于快速且耐氧的自由基光聚合

Aggregation-Induced Emission Photocatalysts for Fast and Oxygen-Tolerant Radical Photopolymerization

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