硫杂石墨烯纳米条带的合成与性质研究

doi:10.6023/cjoc202604043

有机化学 ›› 2026, Vol. 46 ›› Issue (9): 3697-3703.DOI: 10.6023/cjoc202604043 上一篇下一篇

研究论文

硫杂石墨烯纳米条带的合成与性质研究

沈义函^a^,^†, 张瑞影^a^,^b^,^†, 高捷龙^a, 李明港^a, 李远明^a^,^b^,^*(), 叶克印^a^,^*()

^a 福州大学化学学院有机合成与功能福建省高校重点实验室福州 350108
^b 福州大学化学学院能源与环境光催化国家重点实验室福州 350116

收稿日期:2026-04-28 修回日期:2026-06-07 发布日期:2026-07-14
作者简介:
^† 共同第一作者
基金资助:
福建省本科高校教育教学研究重大项目(FBJY20250332); 福州大学研究生教育教学改革研究重点项目(FYCG2025005); 福州大学研究生教育教学改革研究重点项目(FYAI2025019); 福州大学化学学院化学拔尖人才创新训练计划(HXBJ202402)

Synthesis and Properties of Sulfur-Containing Graphene Nanoribbons

Yihan Shen^a, Ruiying Zhang^a^,^b, Jielong Gao^a, Minggang Li^a, Yuanming Li^a^,^b^,^*(), Keyin Ye^a^,^*()

^a Key Laboratory of Molecule Synthesis and Function Discovery, College of Chemical, Fuzhou University, Fuzhou 350108
^b State Key Laboratory of Chemistry for NBC Hazards Protection, State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350116

Received:2026-04-28 Revised:2026-06-07 Published:2026-07-14
Contact:
^* E-mail: yuanming.li@fzu.edu.cn;
kyye@fzu.edu.cn
About author:
Dedicated to the 100th anniversary of the birth of Professor Xikui Jiang.
^† These authors contributed equally to this work
Supported by:
Major Project of Teaching and Education Research for Undergraduate Universities in Fujian Province(FBJY20250332); Key Project of Graduate Education and Teaching Reform Research of Fuzhou University(FYCG2025005); Key Project of Graduate Education and Teaching Reform Research of Fuzhou University(FYAI2025019); Chemistry Top Talent Innovation Training Program of the College of Chemistry, Fuzhou University(HXBJ202402)

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摘要/Abstract

通过铃木-宫浦偶联和肖尔反应, 成功合成了一种具有扭曲结构的硫杂石墨烯纳米条带分子. 将噻吩单元选择性地氧化为砜基团, 能够显著调控该分子的光物理和电化学性质. 进一步采用密度泛函理论计算, 阐明了硫杂石墨烯纳米条带分子及其氧化物的电子激发机制与芳香性特征. 本工作为制备具有可调电子性质的硫掺杂石墨烯纳米带提供了一条简洁高效的合成路线.

关键词: 石墨烯纳米带, 硫掺杂, 电化学合成

A twisted sulfur-doped graphene nanoribbon (GNR) was successfully synthesized via a sequential Suzuki-Miyaura coupling and Scholl reaction. Oxidation of the incorporated thiophene units to sulfone groups was found to be a highly effective molecular engineering strategy, significantly modulating the photophysical and electrochemical properties of the nanoribbon. Density functional theory (DFT) calculations were employed to elucidate the underlying excited-state dynamics and aromatic characteristics. This work establishes a robust and efficient synthetic route for the preparation of sulfur-doped GNRs with precisely tailored electronic properties.

Key words: graphene nanoribbons, sulfur doping, electrochemical synthesis

引用此文

沈义函, 张瑞影, 高捷龙, 李明港, 李远明, 叶克印. 硫杂石墨烯纳米条带的合成与性质研究[J]. 有机化学, 2026, 46(9): 3697-3703.

Yihan Shen, Ruiying Zhang, Jielong Gao, Minggang Li, Yuanming Li, Keyin Ye. Synthesis and Properties of Sulfur-Containing Graphene Nanoribbons[J]. Chinese Journal of Organic Chemistry, 2026, 46(9): 3697-3703.

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图/表 7

Figure 1. (a) Axial π-extension of the sulfur-doping GNRs (The tert-butyl groups are omitted for clarity); (b) Chemical, electrochemical, and e-flow Scholl reactions

Scheme 1. Preparation of sulfur-containing graphene nanoribbons AR-9 and ARO-9 Reaction conditions: Condition 1: compound 4 (0.06 mmol), DDQ (2.4 equiv.), CF3SO3H, CH2Cl2; Condition 2: in an undivided cell, a carbon felt anode, a Pt cathode, compound 4 (0.01 mmol), nBu4NBF4 (0.067 mol/L), V(DCM)∶V(TFA)=4∶1, DDQ (10 mol%), r.t., Ecell=1.65 V, 40 min; Condition 3: in an e-flow reactor, a carbon anode, a Ni cathode, compound 4 (0.01 mmol), nBu4NBF4 (0.1 mol/L), V(DCM)∶V(TFA)=4∶1, DDQ (10 mol%), r.t., Ecell=1.65 V, v=0.12 mL/min. a Yield was determined by 1H NMR with 1,3,5-trimethoxybenzene as the internal standard. b Isolated yield.

Figure 2. CV (solid lines) and DPV (dashed lines) of AR-5 (black), AR-9 (red) and ARO-9 (blue) in DCM solution containing 0.1 mol/L nBu4NBF4 at room temperature at a scan rate of 0.3 V/s

Figure 3. (a) UV-vis absorption (b) fluorescence for AR-5, AR-9 and ARO-9 were obtained at 10－5 mol/L in CH2Cl2

Compd.	λ_abs^a/nm	λ_em^a/nm	E_HOMO^b/eV	E_LUMO^b/eV	E_g^b/eV
AR-5	288/346/362	386	－5.26	－1.26	4.00
AR-9	318/377/398	419/438	－5.21	－1.58	3.64
ARO-9	298/441	509	－5.51	－2.24	3.27

Table 1. Photophysical properties of AR-9 and ARO-9.

Figure 4. (a) Stereoisomers of AR-9 and their relative Gibbs free energies. (b) Calculated Gibbs free energies of 5 for the conversion from the (P, M, P) to the (M, P, M)

Figure 5. (a) NICS(1)av of AR-9 and ARO-9 calculated at B3LYP/6-31＋G(d) level. (b) ACID of AR-9 and ARO-9 calculated at B3LYP/6-31G(d) level

参考文献 34

[1]	Borissov, A.; Maurya, Y. K.; Moshniaha, L.; Wong, W.-S.; Żyła-Karwowska, M.; Stępień, M. Chem. Rev. 2022, 122, 565. doi: 10.1021/acs.chemrev.1c00449
[2]	Wang, M.-W.; Fan, W.; Li, X.; Liu, Y.; Li, Z.; Jiang, W.; Wu, J.; Wang, Z. ACS Nano 2023, 17, 20734. doi: 10.1021/acsnano.3c07970
[3]	Wu, J.; Pisula, W.; Müllen, K. Chem. Rev. 2007, 107, 718. doi: 10.1021/cr068010r
[4]	Zeng, Z.; Shi, X.; Chi, C.; López Navarrete, J. T.; Casado, J.; Wu, J. Chem. Soc. Rev. 2015, 44, 6578. doi: 10.1039/C5CS00051C
[5]	Wang, J.; Wu, Z.-X.; Han, L.-L.; Liu, Y.-Y.; Guo, J.-P.; Xin, H. L.; Wang, D.-L. Chin. Chem. Lett. 2016, 27, 597. doi: 10.1016/j.cclet.2016.03.011
[6]	Wang, X.-Y.; Yao, X.; Narita, A.; Müllen, K. Acc. Chem. Res. 2019, 52, 2491. doi: 10.1021/acs.accounts.9b00322
[7]	Yang, X.; Elbert, S. M.; Rominger, F.; Mastalerz, M. J. Am. Chem. Soc. 2022, 144, 9883. doi: 10.1021/jacs.2c02645
[8]	Zhang, R.; Chen, X.; Zhu, L.; Huang, Y.; Zhai, Z.; Wang, Q.; Wang, L.; Wang, T.; Wang, W.-Z.; Ye, K.-Y.; Li, Y. Chem. Sci. 2025, 16, 7366. doi: 10.1039/D4SC08353A
[9]	Ma, J.; Zhang, H.; Liang, Q.; Han, G.; Shangguan, Z.; Yi, Y.; Zang, Y.; Li, Y.; Zhang, G.; Zhang, X.-S.; Zhang, D. Angew. Chem., Int. Ed. 2026, 65, e5981923. doi: 10.1002/anie.v65.21
[10]	Zhang, L.; Niu, J.; Li, M.; Xia, Z. J. Phys. Chem. C 2014, 118, 3545. doi: 10.1021/jp410501u
[11]	Gopalsamy, K.; Balamurugan, J.; Thanh, T. D.; Kim, N. H.; Lee, J. H. Chem. Eng. J. 2017, 312, 180. doi: 10.1016/j.cej.2016.11.130
[12]	Luo, S.; Chen, X.; He, Y.; Gu, Y.; Zhu, C.; Yang, G.-H.; Qu, L.-L. J. Mater. Chem. B 2021, 9, 6129. doi: 10.1039/D1TB00871D
[13]	Zhang, Y.-F.; Zhang, Y.; Li, G.; Lu, J.; Que, Y.; Chen, H.; Berger, R.; Feng, X.; Müllen, K.; Lin, X.; Zhang, Y.-Y.; Du, S.; Pantelides, S. T.; Gao, H.-J. Nano Res. 2017, 10, 3377. doi: 10.1007/s12274-017-1550-2
[14]	Grzybowski, M.; Skonieczny, K.; Butenschön, H.; Gryko, D. T. Angew. Chem., Int. Ed. 2013, 52, 9900. doi: 10.1002/anie.201210238 pmid: 23852649
[15]	Miao, Q. Nat. Rev. Chem. 2021, 5, 602. doi: 10.1038/s41570-021-00308-y
[16]	Yu, W.; Yang, C.; Feng, X.; Shen, C. Chin. Chem. Lett. 2025, 36, 110939. doi: 10.1016/j.cclet.2025.110939
[17]	Chen, X.-Y.; Li, J.-K.; Wang, X.-Y. Chin. J. Org. Chem. 2021, 41, 4105 (in Chinese). doi: 10.6023/cjoc202107063
	(陈星宇, 李继坤, 王小野, 有机化学, 2021, 41, 4105.) doi: 10.6023/cjoc202107063
[18]	Zhang, Y.; Pun, S. H.; Miao, Q. Chem. Rev. 2022, 122, 14554. doi: 10.1021/acs.chemrev.2c00186
[19]	Röse, P.; Emge, S.; König, C. A.; Hilt, G. Adv. Synth. Catal. 2017, 359, 1359. doi: 10.1002/adsc.v359.8
[20]	Morofuji, T.; Shimizu, A.; Yoshida, J. Angew. Chem., Int. Ed. 2012, 51, 7259.
[21]	Yan, M.; Kawamata, Y.; Baran, P. S. Chem. Rev. 2017, 117, 13230. doi: 10.1021/acs.chemrev.7b00397
[22]	Kingston, C.; Palkowitz, M. D.; Takahira, Y.; Vantourout, J. C.; Peters, B. K.; Kawamata, Y.; Baran, P. S. Acc. Chem. Res. 2020, 53, 72. doi: 10.1021/acs.accounts.9b00539
[23]	Guo, B.; Zhang, J.; Ling, J.-Y.; Tong, Z.-L.; Xie, L.-Y.; Young, D. J.; Xu, H.-C. Green Synth. Catal. 2026, 7, 57.
[24]	Chen, S.; Zhu, X.; Zhang, R.; Wang, W.; Lu, Y.; Wang, Z.; Xu, J.; Ye, K.-Y.; Li, Y.; Yuan, Y. Cryst. Growth Des. 2025, 25, 8593. doi: 10.1021/acs.cgd.5c00966
[25]	Wang, Q.; Wang, W.-Z.; Zhang, R.; Zhai, Z.; Chen, X.; Li, M.; Jin, Y.; Zhu, L.; Li, Y.; Ye, K.-Y. JACS Au 2025, 5, 4281. doi: 10.1021/jacsau.5c00653
[26]	Wang, W.-Z.; Wang, Q.; He, X.; Shen, Y.-H.; Zhai, Z.; Zhang, R.; Li, Y.; Ye, K.-Y. Org. Lett. 2024, 26, 2243. doi: 10.1021/acs.orglett.4c00445
[27]	Huang, J.; Zhu, L.; Wang, T.; Zhang, R.; Huang, Y.; Zhai, Z.; Mei, Y.; Xie, L.; Li, Y. Helv. Chim. Acta 2025, 108, e202500075.
[28]	Li, Y.; Yagi, A.; Itami, K. Chem. Sci. 2019, 10, 5470. doi: 10.1039/C9SC00334G
[29]	Neese, F. Chem. Eur. J. 2023, 29, e202301815.
[30]	Mardirossian, N.; Head-Gordon, M. J. Chem. Phys. 2016, 144, 214110. doi: 10.1063/1.4952647
[31]	Randić, M. Chem. Rev. 2003, 103, 3449. pmid: 12964878
[32]	Chen, Z.; Wannere, C. S.; Corminboeuf, C.; Puchta, R.; Schleyer, P. v. R. Chem. Rev. 2005, 105, 3842. doi: 10.1021/cr030088+
[33]	Geuenich, D.; Hess, K.; Köhler, F.; Herges, R. Chem. Rev. 2005, 105, 3758. pmid: 16218566
[34]	Zeng, L.; Jiao, Y.; Yan, W.; Wu, Y.; Wang, S.; Wang, P.; Wang, D.; Yang, Q.; Wang, J.; Zhang, H.; Lei, A. Nat. Synth. 2023, 2, 172. doi: 10.1038/s44160-022-00197-z

硫杂石墨烯纳米条带的合成与性质研究

Synthesis and Properties of Sulfur-Containing Graphene Nanoribbons

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