非对称联苯基热活化延迟荧光化合物的合成及其发光性质研究

doi:10.6023/cjoc202604042

摘要/Abstract

缺电子的3-硝基-3'-溴-6,6'-二氟联苯二腈与1 equiv.咔唑在碱性条件下发生较为罕见的芳香亲核取代反应, 苯环上的硝基被9-咔唑基取代, 生成3-溴-3'-(9H-咔唑-9-基)-6,6'-二氟-[1,1'-联苯]-2,2'-二腈(1). 3-硝基-3'-溴-6,6'-二氟联苯二腈分别与2 equiv.咔唑或二叔丁基咔唑反应, 硝基和同一个苯环上的氟原子被(二叔丁基)咔唑基取代, 生成3-溴-6-氟-3',6'-二(9H-咔唑-9-基)-[1,1'-联苯]-2,2'-二腈(2a)或3-溴-6-氟-3',6'-二(3,6-二叔丁基-9H-咔唑-9-基)-[1,1'-联苯]-2,2'-二腈(2b). 化合物2a与3-甲酰基苯硼酸发生钯催化的Suzuki偶联反应, 生成3,6-二(9H-咔唑-9-基)-6'-氟-3''-甲酰基-[1,1':3',1''-三联苯]-2,2'-二腈(3). 通过谱学方法、元素分析(2b)、X射线衍射(2a和3)和密度泛函理论(DFT)方法, 研究了几个非对称联苯产物1, 2a, 2b和3的组成和结构, 并对该芳香亲核取代反应的机理进行了讨论. 发光性质研究表明, 化合物1, 2a, 2b和3均具有热活化延迟荧光(TADF)性质. 本文的研究结果为非对称联苯TADF化合物的设计和合成提供了新思路.

关键词: 联苯, 芳香亲核取代, 缺电子, 热活化延迟荧光(TADF)

Under basic conditions, the electron-deficient 3-nitro-3'-bromo-6,6'-difluorodicyanobiphenyl undergoes an uncom-mon nucleophilic aromatic substitution (S_NAr) reaction with 1 equiv. of carbazole, in which the nitro group on the ring is replaced by a 9-carbazolyl group, to afford compound 1. In contrast, in the same reactions with 2 equiv. of carbazole and di-tert-butylcarbazole, respectively, the nitro group and the fluorine atom on the same benzene ring are substituted by 9-carba-zolyl or 9-di-tert-butylcarbazolyl to produce 3',6'-bis(9H-carbazol-9-yl)-[1,1'-biphenyl]-2,2'-dicyanide (2a) and 3-bromo-6-fluoro-3',6'-bis(3,6-di-t-butyl-9H-carbazol-9-yl)-[1,1'-biphenyl]-2,2'-dicyanide (2b). Compound 2a undergoes a Pd-catalyzed Suzuki coupling with 3-formylphenylboronic acid to give 3,6-bis(9H-carbazol-9-yl)-6'-fluoro-3''-formyl-[1,1':3',1''-terphenyl]-2,2'-dicyanide (3). The structures and compositions of the products have been studied using spectroscopic methods, elemental analysis (2b), X-ray diffraction (2a and 3), as well as density functional theory (DFT) calculations, and the mechanism of the S_NAr reaction is discussed. Investigations on the emission properties show that compounds 1, 2a, 2b, and 3 exhibit thermally activated delayed fluorescence (TADF) properties. These results provide new ideas for the design and synthesis of asymmetric biphenyl TADF compounds.

Key words: biphenyl, nucleophilic aromatic substitution (S_NAr), electron-deficient, thermally activated delayed fluorescence (TADF)

引用此文

张雪玥, 李丹, 苗金玲, 李德利, 刘广宁, 蒋绪川, 聂永. 非对称联苯基热活化延迟荧光化合物的合成及其发光性质研究[J]. 有机化学, 2026, 46(10): 4023-4033.

Xueyue Zhang, Dan Li, Jinling Miao, Deli Li, Guangning Liu, Xuchuan Jiang, Yong Nie. Synthesis and Emission Properties of Unsymmetric Biphenyl-Based Thermally Activated Delayed Fluorescence Compounds[J]. Chinese Journal of Organic Chemistry, 2026, 46(10): 4023-4033.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 15

图1. (a)对称型和(b)非对称型的联苯TADF化合物, 以及(c)本文研究的非对称型联苯TADF化合物

Figure 1. Symmetric (a) and unsymmetric (b) biphenyl TADF compounds, as well as the unsymmetric biphenyl TADF compounds (c) in this work

图2. 三种缺电子联苯化合物的结构式

Figure 2. Chemical structures of three electron-deficient biphenyl compounds

图式1. 联苯化合物1, 2a, 2b和3的合成

Scheme 1. Synthesis of compounds 1, 2a, 2b, and 3

图3. 化合物C和1环上碳原子的Mulliken电荷

Figure 3. Mulliken charges of ring carbon atoms of compounds C and 1

图4. (a)化合物2a(两个晶体学独立分子中的分子A)的单晶结构(椭球概率为50%, 省略氢原子); (b)部分二面角

Figure 4. (a) Crystal structure of compound 2a (one of the two crystallographically independent molecules A is shown, hydrogen atoms are omitted for clarity, thermal ellipsoids are drawn at 50% probability); (b) Some dihedral angles

图5. 化合物2a分子间的相互作用(数值为原子间距离或原子到平面重心间距)

Figure 5. Intermolecular interactions in compound 2a (the values are those for interatomic or atom-centroid distances)

图6. (a)化合物3的单晶结构(椭球概率为50%, 氢原子未画出); (b)部分二面角

Figure 6. (a) Crystal structure of compound 3 (hydrogen atoms are omitted for clarity, thermal ellipsoids are drawn at 50% probability); (b) Some dihedral angles

图7. 化合物3分子间的相互作用(数值为原子间距离或原子到平面重心间距)

Figure 7. Intermolecular interactions in compound 3 (the values are those for interatomic or atom-centroid distances)

图8. 化合物1, 2a, 2b和3的前线分子轨道、能级差及单重态-三重态能级差(B3LYP/6-31G (d,p)水平)

Figure 8. Frontier molecular orbitals and energy levels of compounds 1, 2a, 2b, and 3 (B3LYP/6-31G (d,p) level)

图9. 化合物1, 2a, 2b, 3的紫外-可见光谱(甲苯, c=1×10-5 mol/L)

Figure 9. UV-Vis spectra of compounds 1, 2a, 2b, and 3 (toluene, c=1×10-5 mol/L)

Compd.	λ_abs^a/nm	λ_em^a/nm	FWHM^a/nm	λ_em^b/nm	FWHM^b/nm	λ_em^c/nm	FWHM^c/nm	Φ^b	τ_PF/ns^c	τ_D_F^c/µs	k_RISC^c^,^d/s^-1
1	286, 332	455	74	442	93	454	80	26%	7.0	17.3	4.2×10⁵
2a	285, 330	452	72	459	69	451	76	34%	5.9	29.5	3.4×10⁵
2b	291, 335	462	76	476	68	469	83	59%	8.6	12.4	2.4×10⁵
3	285, 330	441	66	457	72	439	76	43%	8.4	14.9	1.0×10⁵

表1. 化合物1, 2a, 2b, 3的光物理数据

Table 1. Photophysical data of compounds 1, 2a, 2b, and 3

图10. 化合物1, 2a, 2b, 3在甲苯溶液中的归一化荧光光谱

Figure 10. Fluorescence spectra of 1, 2a, 2b, and 3 in different solvents at room temperature c=1×10-5 mol/L. 1: λex=300 nm, 2a: λex=332 nm, 2b: λex=330 nm, 3: λex=310 nm.

Solvent	1	2a	2b	3
Hexane	427	432	454	428
Toluene	455	452	462	441
Tetrahydrofuran	484	470	494	458
Ethyl acetate	483	468	498	457
Dichloromethane	486	475	508	462
Acetonitrile	518	506	540	488

表2. 室温下化合物1, 2a, 2b, 3在不同溶剂中的最大发射波长

Table 2. Emission maxima (nm) of compounds 1, 2a, 2b, and 3 in different solvents at room temperature

μ/Debye	1	2a	2b	3
S₀	4.95	4.75	4.57	4.54
S₁	14.23	14.95	16.80	11.05

表3. 化合物1, 2a, 2b, 3的S0和S1态的偶极矩

Table 3. Dipole moments of compounds 1, 2a, 2b, and 3 at S0 and S1 states

图11. 化合物1, 2a, 2b, 3的固体荧光光谱(λex=330 nm)

Figure 11. Fluorescence emission spectra of compounds 1, 2a, 2b, and 3 in solid state (λex=330 nm) Insets are photos of the samples under natural light (a, c, e, g) and UV light at 365 nm (b, d, f, h). a, b for compound 1, c, d for compound 2a, e, f for compound 2b, and g, h for compound 3.

参考文献 21

[1]	(a) Gangadhar P. S.; Reddy G.; Prasanthkumar S.; Giribabu L. Phys. Chem. Chem. Phys. 2021, 23, 14969. doi: 10.1039/d1cp01185e pmid: 34231592
	(b) Fang M.; Yang J.; Li Z. Prog. Mater. Sci. 2022, 125, 100914. doi: 10.1016/j.pmatsci.2021.100914 pmid: 34231592
[2]	Tang C. W.; Vanslyke S. A. Appl. Phys. Lett. 1987, 51, 913. doi: 10.1063/1.98799
[3]	Uoyama H.; Goushi K.; Shizu K.; Nomura H.; Adachi C. Nature 2012, 492, 234. doi: 10.1038/nature11687
[4]	(a) Dos Santos J. M.; Hall D.; Basumatary B.; Bryden M.; Chen D.; Choudhary P.; Comerford T.; Crovini E.; Danos A.; De J.; Diesing S.; Fatahi M.; Griffin M.; Gupta A. K.; Hafeez H.; Hämmerling L.; Hanover E.; Haug J.; Heil T.; Karthik D.; Kumar S.; Lee O.; Li H.; Lucas F.; Mackenzie C. F. R.; Mariko A.; Matulaitis T.; Millward F.; Olivier Y.; Qi Q.; Samuel I. D. W.; Sharma N.; Si C.; Spierling L.; Sudhakar P.; Sun D.; Tankelevičiūtė E.; Duarte Tonet M.; Wang J.; Wang T.; Wu S.; Xu Y.; Zhang L.; Zysman C. E. Chem. Rev. 2024, 124, 13736. doi: 10.1021/acs.chemrev.3c00755
	(b) Cai X. Y.; Su S. J. Adv. Funct. Mater. 2018, 28, 1802558. doi: 10.1002/adfm.v28.43
[5]	Li M.; Wang M. Y.; Wang Y. F.; Feng L.; Chen C. F. Angew. Chem. Int. Ed. 2021, 60, 20728. doi: 10.1002/anie.v60.38
[6]	Tan J. H.; Huo Y. P.; Cai N.; Ji S. M.; Li Z. Z.; Zhang L. Chin. J. Org. Chem. 2017, 37, 2457 (in Chinese).
	(谭继华, 霍延平, 蔡宁, 季少民, 李宗志, 张力, 有机化学, 2017, 37, 2457.) doi: 10.6023/cjoc201704015
[7]	(a) Tu Z. L.; Yan Z. P.; Liang X.; Chen L.; Wu Z. G.; Wang Y.; Zheng Y. X.; Zuo J. L.; Pan Y. Adv. Sci. 2020, 7, 2000804. doi: 10.1002/advs.v7.15
	(b) Li M.; Wang Y. F.; Zhang D.; Duan L.; Chen C. F. Angew. Chem. Int. Ed. 2020, 59, 3500. doi: 10.1002/anie.v59.9
	(c) Chen J.; Zhang X.; Xie Z.; Liu B. Aggregate 2024, 5, e638.
[8]	(a) Zhao W. L.; Tan K. K.; Guo W. C.; Guo C. H.; Li M.; Chen C. F. Adv. Sci. 2024, 11, 2309031. doi: 10.1002/advs.v11.23
	(b) Tan K. K.; Zhang D. W.; Zhao W. L.; Li M.; Chen C. F. Chem. Eng. J. 2023, 462, 142123. doi: 10.1016/j.cej.2023.142123
	(c) Wang Y. F.; Li M.; Zhao W. L.; Shen Y. F.; Lu H. Y.; Chen C. F. Chem. Commun. 2020, 56, 9380. doi: 10.1039/D0CC03822A
	(d) Yang X. D.; Zheng X. K.; Dong H. L.; Sun J.; Wang H. Chin. J. Org. Chem. 2023, 43, 1292 (in Chinese). doi: 10.6023/cjoc202208023
	(杨晓东, 郑小康, 董海亮, 孙静, 王华, 有机化学, 2023, 43, 1292.) doi: 10.6023/cjoc202208023
[9]	(a) Lin T.; Xie J.; Zhou Y.; Zhou Y.; Yuan Y.; Fan F.; Wen S. Crystals 2021, 11, 900. doi: 10.3390/cryst11080900
	(b) Yuan W.; Hu W.; Wang J.; Zhu M.; Shi C.; Sun N.; Tao Y. Chin. J. Chem. 2023, 41, 1829. doi: 10.1002/cjoc.v41.15
[10]	(a) Zhang D. W.; Li M.; Chen C. F. Chem. Soc. Rev. 2020, 49, 1331. doi: 10.1039/C9CS00680J pmid: 26967372
	(b) Yan Z. P.; Yuan L.; Zhang Y.; Mao M. X.; Liao X. J.; Ni H. X.; Wang Z. H.; An Z.; Zheng Y. X.; Zuo J. L. Adv. Mater. 2022, 34, e2204253. pmid: 26967372
	(c) Feuillastre S.; Pauton M.; Gao L.; Desmarchelier A.; Riives A. J.; Prim D.; Tondelier D.; Geffroy B.; Muller G.; Clavier G.; Pieters G. J. Am. Chem. Soc. 2016, 138, 3990. doi: 10.1021/jacs.6b00850 pmid: 26967372
[11]	(a) Feng C.; Zhang K.; Zhang B.; Feng L.; He L.; Chen C. F.; Li M. Angew. Chem. Int. Ed. 2025, 64, e202425094.
	(b) Wang X. Z.; Xing S.; Xiao X.; Yuan L.; Hou Z. Y.; Zheng Y. X. Adv. Funct. Mater. 2025, 35, 2412044. doi: 10.1002/adfm.v35.1
	(c) Zhang D. W.; Li M.; Chen C. F. Angew. Chem. Int. Ed. 2022, 61, e202213130.
	(d) Zhang D. W.; Li M.; Chen C. F. Sci. China Mater. 2023, 66, 4030. doi: 10.1007/s40843-023-2551-y
	(e) Wan S. P.; Zhao W. L.; Tan K. K.; Lu H. Y.; Li M. Chem. Eng. J. 2023, 468, 143508. doi: 10.1016/j.cej.2023.143508
	(f) Guo C. H.; Zhao W. L.; Tan K. K.; Guo W. C.; Feng L.; Chen C. F.; Li M. Sci. China Chem. 2024, 67, 2039. doi: 10.1007/s11426-024-2017-8
	(g) Tu Z. L.; Lu J. J.; Luo X. F.; Hu J. J.; Li S.; Wang Y.; Zheng Y. X.; Zuo J. L.; Pan Y. Adv. Optical Mater. 2021, 9, 2100596. doi: 10.1002/adom.v9.20
	(h) Gao S. L.; Zhang X. Y.; Yan P. Z.; Miao J. L.; Liu G. N.; Jiang X. C.; Nie Y.; Li M. Z. Naturforsch. B 2025, 80, 191. doi: 10.1515/znb-2025-0004
[12]	(a) Liu G.; Yan Z.; Song Q.; Sun Q.; Xue S.; Yang W. ACS Macro Lett. 2025, 14, 265. doi: 10.1021/acsmacrolett.4c00818
	(b) Xia W.; Ye Z.; Wu G.; Yao H.; Gao H.; Xu B.; Chong Q.; Zhang K. Angew. Chem. Int. Ed. 2025, 64, e202518387.
	(c) Su N.; Wang J.; Yang Y.; Yan Z.; Zhou L.; Zheng Y. X.; Ding J. Angew. Chem. Int. Ed. 2025, 64, e202512717.
[13]	Beier P.; Pastýříková T.; Vida N.; Iakobson G. Org. Lett. 2011, 13, 1466. doi: 10.1021/ol2001478 pmid: 21341714
[14]	Zhang D. W.; Teng J. M.; Wang Y. F.; Han X. N.; Li M.; Chen C. F. Mater. Horiz. 2021, 8, 3417. doi: 10.1039/D1MH01404H
[15]	Kielmann M.; Flanagan K. J.; Norvaiša K.; Intrieri D.; Senge M. O. J. Org. Chem. 2017, 82, 5122. doi: 10.1021/acs.joc.7b00328 pmid: 28452490
[16]	Manley King C. I.; Bergh J. J.; Petzer J. P. Bioorg. Chem. 2012, 40, 114. doi: 10.1016/j.bioorg.2011.10.003 pmid: 22100142
[17]	Frisch M. J.; Trucks G. W.; Schlegel H. B.; Scuseria G. E.; Robb M. A.; Cheeseman J. R.; Scalmani G.; Barone V.; Mennucci B.; Petersson G. A.; Nakatsuji H.; Caricato M.; Li X.; Hratchian H. P.; Izmaylov A. F.; Bloino J.; Zheng G.; Sonnenberg J. L.; Hada M.; Ehara M.; Toyota K.; Fukuda R.; Hasegawa J.; Ishida M.; Nakajima T.; Honda Y.; Kitao O.; Nakai H.; Vreven T.; Montgomery Jr., J. A.; Peralta J. E.; Ogliaro F.; Bearpark M.; Heyd J. J.; Brothers E.; Kudin K. N.; Staroverov V. N.; Kobayashi R.; Normand J.; Raghavachari K.; Rendell A.; Burant J. C.; Iyengar S. S.; Tomasi J.; Cossi M.; Rega N.; Millam J. M.; Klene M.; Knox J. E.; Cross J. B.; Bakken V.; Adamo C.; Jaramillo J.; Gomperts R.; Stratmann R. E.; Yazyev O.; Austin A. J.; Cammi R.; Pomelli C.; Ochterski J. W.; Martin R. L.; Morokuma K.; Zakrzewski V. G.; Voth G. A.; Salvador P.; Dannenberg J. J.; Dapprich S.; Daniels A. D.; Farkas O.; Foresman J. B.; Ortiz J. V.; Cioslowski J.; Fox D. J. Gaussian 09, Revision A.02, Gaussian, Inc., Wallingford CT, 2009.
[18]	Li M.; Chen C.-F. Org. Chem. Front. 2022, 9, 6441. doi: 10.1039/D2QO01383E
[19]	Nakagawa T.; Ku S.; Wong K.; Adachi C. Chem. Commun. 2012, 48, 9580. doi: 10.1039/c2cc31468a
[20]	(a) Ma Z.; Tu J.; Yang D.; Zhang Q.; Wu J. J. Mol. Struct. 2024, 1312, 138478. doi: 10.1016/j.molstruc.2024.138478
	(b) Huber A.; Dubbert J.; Scherz T. D.; Voskuhl J. Chem. Eur. J. 2023, 29, e202202481.
[21]	Zhu H.; Li M.; Hu J.; Wang X.; Jie J.; Guo Q.; Chen C.; Xia A. Sci. Rep. 2016, 6, 24313. doi: 10.1038/srep24313