供体-受体-供体(D-A-D)型芳香酮设计合成与光催化C(sp3)—H偶联反应性能研究

doi:10.6023/cjoc202501013

摘要/Abstract

设计合成了一系列以二酰基四氟苯为电子受体中心, 两侧连接多取代芳基为电子供体基团的供体-受体-供体(D-A-D)型芳香酮光敏剂(PC3~PC8), 并成功应用于甲基芳烃与芳基溴化物的C(sp³)—H偶联反应的光催化体系. 研究结果表明, 以间位二酰基四氟苯为电子受体中心, 以均三甲苯为供体基团的PC8表现出优异光催化性能, 其活性相比传统二苯甲酮提升460倍. 更值得注意的是, 成功活化了固态甲基芳烃类底物, 突破了甲基芳烃作反应溶剂的关键限制, 显著拓展了底物适用性范围. 理论计算表明, 光敏剂PC8的D-A-D结构能有效分离最高占据分子轨道(HOMO)与最低未占据分子轨道(LUMO)的电子云分布, 从而降低单重态-三重态能隙(ΔE_S-T), PC8的ΔE_S-T值(1.48 eV)明显低于二苯甲酮(1.84 eV), 有利于系间窜越(ISC)过程. 吸收光谱表明PC8在310 nm有特征吸收峰, 稳态荧光分析进一步证实, PC8的荧光量子效率为二苯甲酮的5倍, 上述光谱表征结果表明, PC8具有较好的光物理性能, 有效地促进了光催化循环的量子效率提升.

关键词: 芳香酮光敏剂, 光催化, C(sp³)—H活化, 偶联反应, 量子效率

A series of donor-acceptor-donor (D-A-D) aromatic ketone photosensitizers (PC3~PC8) were successfully designed and synthesized. These compounds feature a diacyltetrafluorobenzene electron-acceptor core connected with multi- substituted aryl electron-donor groups on both sides. They demonstrated excellent performance at photocatalytic systems for C(sp³)—H coupling reactions between methylarenes and aryl bromides. The study found that PC8, which uses meta-diacyl- tetrafluorobenzene as the electron-acceptor core and mesitylene as donor groups, shows outstanding photocatalytic performance. Its activity is 460 times higher than traditional benzophenone. More notably, this work reported the activation of solid methylarene substrates, which overcame the key limitation of using methylarenes solely as reaction solvents and significantly broadened the substrate scope. Theoretical calculations revealed that the D-A-D structure of photosensitizer PC8 effectively separates the electron density distributions of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). This reduces the singlet-triplet energy gap (ΔE_S-T). The ΔE_S-T value of PC8 (1.48 eV) is significantly lower than that of benzophenone (1.84 eV), which facilitates the intersystem crossing (ISC) process. The absorption spectra revealed that PC8 has a characteristic absorption peak at 310 nm. Steady-state fluorescence analysis further proved that PC8 has 5 times higher fluorescence quantum yield than benzophenone. These spectroscopic characterizations demonstrate that PC8 possesses superior photophysical properties, effectively driving the enhancement of quantum efficiency in the photocatalytic cycle.

Key words: aromatic ketone photosensitizer, photocatalysis, C(sp³)—H activation, coupling reaction, quantum efficiency

引用此文

祝辉, 吴鹏, 钟晨鸣, 李舒铭, 林钢, 刘雪粉, 罗书平. 供体-受体-供体(D-A-D)型芳香酮设计合成与光催化C(sp³)—H偶联反应性能研究[J]. 有机化学, 2025, 45(9): 3441-3449.

Hui Zhu, Peng Wu, Chenming Zhong, Shuming Li, Gang Lin, Xuefen Liu, Shuping Luo. Design and Synthesis of Donor-Acceptor-Donor (D-A-D) Type Aromatic Ketones for Photocatalytic C(sp³)—H Coupling Reactions[J]. Chinese Journal of Organic Chemistry, 2025, 45(9): 3441-3449.

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图/表 10

图1. (A)芴酮光催化Diels-Alder反应; (B)可见光驱动合成高取代吡咯; (C)异喹啉衍生的二芳基酮型光催化剂催化脱氢偶联; (D)对溴苯腈与甲苯的芳基偶联; (E)甲苯衍生物的C—S功能化

Figure 1. (A) Fluorenone photocatalytic Diels-Alder reaction; (B) visible light-driven synthesis of highly substituted pyrroles; (C) isoquinoline-derived diaryl ketone-based photocatalysts for catalytic dehydrogenation coupling; (D) aryl coupling of p-bromobenzonitrile with toluene; (E) C—S functionalisation of toluene derivatives

图2. 化合物PC1~PC8的结构

Figure 2. Structures of compounds PC1~PC8

Entry	Photocatalyst (mol%)	Solvent	Base		Time/h	Yield^b/%
1	PC1 (20)	Toluene	NaHCO₃		18	30
2^c	—	Toluene	NaHCO₃		18	None
3	PC2 (20)	Toluene	NaHCO₃		18	92
4	PC3 (20)	Toluene	NaHCO₃		18	93
5	PC4 (20)	Toluene	NaHCO₃		18	33
6	PC5 (20)	Toluene	NaHCO₃		18	79
7	PC6 (20)	Toluene	NaHCO₃		18	57
8	PC7 (20)	Toluene	NaHCO₃		18	79
9	PC8 (20)	Toluene	NaHCO₃		18	99
10	PC8 (5)	Toluene	NaHCO₃		18	99
11^d	PC8 (5)	Toluene	NaHCO₃	18		None
12^e	PC8 (5)	Toluene	NaHCO₃		18	None
13^f	PC8 (5)	Toluene	NaHCO₃		18	None
14	PC8 (5)	Toluene	NaHCO₃		10	99
15	PC8 (5)	Toluene	K₂HPO₄		10	84
16	PC8 (5)	Toluene	CH₃COONa		10	23
17	PC8 (5)	Toluene	K₂CO₃		10	33
18	PC8 (5)	Toluene	Na₂CO₃		10	56
19	PC8 (5)	Toluene	NaHCO₃		0.5	96
20	PC8 (5)	DMSO (0.1 mol/L)	NaHCO₃		18	None
21	PC8 (5)	Hexane (0.1 mol/L)	NaHCO₃		18	Trace
22	PC8 (5)	EtOAc (0.1 mol/L)	NaHCO₃		18	7
23	PC8 (5)	MeCN (0.1 mol/L)	NaHCO₃		18	32
24	PC8 (5)	MeCN (0.2 mol/L)	NaHCO₃		18	55
25	PC8 (5)	MeCN (0.4 mol/L)	NaHCO₃		18	99
26	PC8 (5)	MeCN (0.4 mol/L)	NaHCO₃		0.5	87

表1. 光催化甲苯与溴苯的C(sp3)—H偶联反应条件优化a

Table 1. Reaction conditions for photocatalytic C(sp3)—H coupling reaction of toluene with bromobenzene

图3. 甲基芳烃与芳基溴化物的底物拓展a,b

Figure 3. Substrate scope of methylarenes and aryl bromides a Reaction conditions: a mixture of 2a (0.4 mmol, 1.0 equiv.), NaHCO3 (0.8 mmol, 2.0 equiv.), NiCl2•6H2O (0.02 mmol, 5 mol%), PC8 (5 mol%), and dtbbpy (0.02 mmol, 5 mol%), in solvents (5 mL) was stirred at room temperature irradiated by 20 W blue LEDs under an Ar atmosphere for 0.5 h. b Product yield determined by HPLC using diethyl phthalate as the internal standard; c Acetonitrile/benzene (V:V=3:1) replaced pure acetonitrile. d Temperature was 50 ℃. e K3PO4 instead of NaHCO3.

图4. PC1~PC8的紫外吸收光谱图

Figure 4. UV absorption spectra of PC1~PC8

图5. PC1~PC8的荧光发射光谱图

Figure 5. Fluorescence emission spectra of PC1~PC8

图6. (a) PC8的几何形状; (b) PC8的HOMO轨道定位; (c) PC8的LUMO轨道定位

Figure 6. (a) Geometry of PC8; (b) HOMO orbital localization for PC8; (c) LUMO orbital localization for PC8

Entry	PC	E_LUMO/eV	E_HOMO/eV	ΔE/eV	ΔE_S-T/eV
1	PC1	-2.08	-6.86	4.78	1.84
2	PC2	-2.76	-7.76	5.00	2.06
3	PC3	-2.64	-7.57	4.94	2.00
4	PC8	-2.50	-6.92	4.42	1.48

表2. DFT计算

Table 2. Density functional theory (DFT) calculations

图7. 苄基自由基捕获实验

Figure 7. Experiment of free benzyl radical capture

图8. 光催化芳甲基与芳基溴化物的C(sp3)—H偶联反应可能的机理

Figure 8. Possible mechanism for the photocatalytic C(sp3)—H coupling reaction of arylmethyl groups with aryl bromides

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供体-受体-供体(D-A-D)型芳香酮设计合成与光催化C(sp³)—H偶联反应性能研究

Design and Synthesis of Donor-Acceptor-Donor (D-A-D) Type Aromatic Ketones for Photocatalytic C(sp³)—H Coupling Reactions

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