Citation: Yongjiu Lei, Xu Wang, Zhiye Wang, Jianghao Zhou, Haijian Chen, Lei Liang, Yunchuan Li, Bohuai Xiao, Shuai Chang. Effect of Modified Thiophene Anchor on Molecule-Electrode Bonding[J]. Acta Physico-Chimica Sinica, ;2023, 39(11): 221202. doi: 10.3866/PKU.WHXB202212023 shu

Effect of Modified Thiophene Anchor on Molecule-Electrode Bonding

School of Materials and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081, China

Corresponding author: Yunchuan Li, yc.l@wust.edu.cn Bohuai Xiao, xiaobhuai@foxmail.com Shuai Chang, schang23@wust.edu.cn
Received Date: 14 December 2022
Revised Date: 27 February 2023
Accepted Date: 28 February 2023
Available Online: 9 March 2023
Fund Project: the Outstanding Young and Middle-aged Technical Innovation Team Project in Hubei Universities T2021002the South China University of Technology State Key Laboratory of Luminescent Materials and Devices Open Fund 2022-skllmd-19

The anchor group of a molecule determines its binding characteristics with electrodes. It impacts the molecular conductance of the formed single molecule junctions and is of great importance to the field of molecular electronics. Thiophene unit is an emerging anchor ligand and shows the ability to bind with Au electrodes. As a building block in designing organic photoelectric materials, thiophene has a potential in expanding the variety of target molecules in single-molecule electronics. In this work, we designed and synthesized three analogous π-conjugated molecules, 1, 4-di(thiophen-2-yl)benzene (BT-H), 1, 4-bis(5 hexylthiophen-2-yl)benzene (BT-Hex) and 1, 4-bis(5-chlorothiophen-2-yl)benzene (BT-Cl). These molecules have the same backbone, but different substituents (H, C6 and Cl atoms, respectively) at position 4 of both end-capped thiophenes. Enabled by thiophene anchors, these molecules can be readily incorporated into the nano gaps between electrodes to form molecular junctions. Charge transport properties of three types of single molecule junctions are explored using scanning tunneling microscopy based break junction (STM-BJ) technique and the influence of different substituents at thiophene on the molecule-electrode binding modes are comparatively studied. Two separate binding modes with a conductance discrepancy of more than an order of magnitude are observed for all three molecules, with a high conductance state (G_H) corresponding to a Au—π linked junction (Au electrode coupled with the thiophene π orbital) and a low conductance state (G_L) originating from a Au—S binding scheme. Interestingly, the values of the G_L state for three molecules are greatly affected by the different substituents at thiophenes, yielding a conductance trend of G_BT-Hex > G_BT-H > G_BT-Cl. This can be explained by the electron affinity of different substituents, which shifts their highest occupied molecular orbital (HOMO) with respect to Au Fermi level and thus changes the energy barrier. In contrast, the G_H state values of three molecules are not affected obviously by different substituents. We also statistically analyzed the formation rate of two binding modes for three molecules and found that the ratio between two binding modes can be changed with different addition of substituents. This work provides a useful method in modifying the binding properties of thiophene as an anchor group to gold and sheds light on a simple strategy in the design of anchor ligands.
- Single molecule conductance,
- Molecular configuration,
- Substituent group,
- Thiophene,
- Scanning tunneling microscope break junction
1. [1]
  Buchanan, M. Nat. Phys. 2016, 12 (3), 200. doi: 10.1038/nphys3685 doi: 10.1038/nphys3685
2. [2]
  Yang, Y.; Liu, J. Y.; Yan, R. W.; Wu, D. Y.; Tian, Z. Q. Chem. J. Chin. Univ. 2015, 36 (1), 9. doi: 10.7503/cjcu20140941
3. [3]
  Yu, P. K.; Feng, A. N.; Zhao, S. Q.; Wei, J. Y.; Yang, Y.; Shi, J.; Hong, W. J. Acta Phys. -Chim. Sin. 2019, 35 (8), 829. doi: 10.3866/PKU.WHXB201811027
4. [4]
  Diez-Perez, I.; Hihath, J.; Lee, Y.; Yu, L. P.; Adamska, L.; Kozhushner, M. A.; Oleynik, II; Tao, N. J. Nat. Chem. 2009, 1 (8), 635. doi: 10.1038/nchem.392 doi: 10.1038/nchem.392
5. [5]
  Daaoub, A.; Sangtarash, S.; Sadeghi, H. Nanomaterials 2020, 10 (8), 7. doi: 10.3390/nano10081544 doi: 10.3390/nano10081544
6. [6]
  Quek, S. Y.; Kamenetska, M.; Steigerwald, M. L.; Choi, H. J.; Louie, S. G.; Hybertsen, M. S.; Neaton, J. B.; Venkataraman, L. Nat. Nanotechnol. 2009, 4 (4), 230. doi: 10.1038/nnano.2009.10 doi: 10.1038/nnano.2009.10
7. [7]
  Komoto, Y.; Fujii, S.; Iwane, M.; Kiguchi, M. J. Mater. Chem. C 2016, 4 (38), 8842. doi: 10.1039/c6tc03268k doi: 10.1039/c6tc03268k
8. [8]
  Mathew, P. T.; Fang, F. Engineering 2018, 4 (6), 760. doi: 10.1016/j.eng.2018.11.001 doi: 10.1016/j.eng.2018.11.001
9. [9]
  Chen, Y. R.; Huang, L. F.; Chen, H.; Chen, Z. X.; Zhang, H. W.; Xiao, Z. Y.; Hong, W. J. Chin. J. Chem. 2021, 39 (2), 421. doi: 10.1002/cjoc.202000420 doi: 10.1002/cjoc.202000420
10. [10]
  Chen, F.; Li, X.; Hihath, J.; Huang, Z.; Tao, N. J. J. Am. Chem. Soc. 2006, 128 (49), 15874. doi: 10.1021/ja065864k doi: 10.1021/ja065864k
11. [11]
  Ie, Y.; Tanaka, K.; Tashiro, A.; Lee, S. K.; Testai, H. R.; Yamada, R.; Tada, H.; Aso, Y. J. Phys. Chem. Lett. 2015, 6 (18), 3754. doi: 10.1021/acs.jpclett.5b01662 doi: 10.1021/acs.jpclett.5b01662
12. [12]
  Kaliginedi, V.; Rudnev, A. V.; Moreno-Garcia, P.; Baghernejad, M.; Huang, C. C.; Hong, W. J.; Wandlowski, T. Phys. Chem. Chem. Phys. 2014, 16 (43), 23529. doi: 10.1039/c4cp03605k doi: 10.1039/c4cp03605k
13. [13]
  Sebera, J.; Lindner, M.; Gasior, J.; Meszaros, G.; Fuhr, O.; Mayor, M.; Valasek, M.; Kolivoska, V.; Hromadova, M. Nanoscale 2019, 11 (27), 12959. doi: 10.1039/c9nr04071d doi: 10.1039/c9nr04071d
14. [14]
  Huang, Z.; Chen, F.; Bennett, P. A.; Tao, N. J. J. Am. Chem. Soc. 2007, 129 (43), 13225. doi: 10.1021/ja074456t doi: 10.1021/ja074456t
15. [15]
  Xie, Z. T.; Baldea, I.; Haugstad, G.; Frisbie, C. D. J. Am. Chem. Soc. 2019, 141 (1), 497. doi: 10.1021/jacs.8b11248 doi: 10.1021/jacs.8b11248
16. [16]
  Ohto, T.; Inoue, T.; Stewart, H.; Numai, Y.; Aso, Y.; Ie, Y.; Yamada, R.; Tada, H. J. Phys. Chem. Lett. 2019, 10 (18), 5292. doi: 10.1021/acs.jpclett.9b02059 doi: 10.1021/acs.jpclett.9b02059
17. [17]
  Xu, Y. X.; Sun, L. Y.; Wu, J. F.; Ye, W. Y.; Chen, Y. S.; Zhang, S. M.; Miao, C. Y.; Huang, H. Dyes Pigment. 2019, 168, 36. doi: 10.1016/j.dyepig.2019.04.050 doi: 10.1016/j.dyepig.2019.04.050
18. [18]
  Byeon, S. Y.; Han, S. H.; Lee, J. Y. Dyes Pigment. 2018, 155, 114. doi: 10.1016/j.dyepig.2018.03.033 doi: 10.1016/j.dyepig.2018.03.033
19. [19]
  Oniwa, K.; Kikuchi, H.; Shimotani, H.; Ikeda, S.; Asao, N.; Yamamoto, Y.; Tanigaki, K.; Jin, T. N. Chem. Commun. 2016, 52 (26), 4800. doi: 10.1039/c6cc00948d doi: 10.1039/c6cc00948d
20. [20]
  Zhou, J.; Yang, Y. X.; Liu, P.; Camillone, N.; White, M. G. J. Phys. Chem. C 2010, 114 (32), 13670. doi: 10.1021/jp1025009 doi: 10.1021/jp1025009
21. [21]
  Mao, J. -C.; Peng, L. -L.; Li, W. -Q.; Chen, F.; Wang, H. -G.; Shao, Y.; Zhou, X. -S.; Zhao, X. -Q.; Xie, H. -J.; Niu, Z. -J. J. Phys. Chem. C 2017, 121 (3), 1472. doi: 10.1021/acs.jpcc.6b10925 doi: 10.1021/acs.jpcc.6b10925
22. [22]
  Huang, M.; Dong, J.; Wang, Z.; Li, Y.; Yu, L.; Liu, Y.; Qian, G.; Chang, S. Chem. Commun. 2020, 56 (94), 14789. doi: 10.1039/d0cc05602b doi: 10.1039/d0cc05602b
23. [23]
  Huang, M.; Zhou, Q.; Liang, F.; Yu, L.; Xiao, B.; Li, Y.; Zhang, M.; Chen, Y.; He, J.; Xiao, S.; et al. Nano Lett. 2021, 21 (12), 5409. doi: 10.1021/acs.nanolett.1c01882 doi: 10.1021/acs.nanolett.1c01882
24. [24]
  Chen, H.; Li, Y.; Chang, S. Anal. Chem. 2020, 92 (9), 6423. doi: 10.1021/acs.analchem.9b05549 doi: 10.1021/acs.analchem.9b05549
25. [25]
  Wang, Z.; Huang, M.; Dong, J.; Wang, X.; Li, Y.; Sun, M.; Chang, S. J. Phys. Chem. C 2023, 127 (5), 2518. doi: 10.1021/acs.jpcc.2c06683 doi: 10.1021/acs.jpcc.2c06683
26. [26]
  Li, Y.; Xiao, B.; Chen, R.; Chen, H.; Dong, J.; Liu, Y.; Chang, S. Chem. Commun. 2019, 55 (57), 8325. doi: 10.1039/c9cc02998b doi: 10.1039/c9cc02998b
27. [27]
  Hua, Y.; Zhang, H.; Xia, H. Chin. J. Org. Chem. 2018, 38 (1), 11. doi: 10.6023/cjoc201709009
28. [28]
  Moellmann, J.; Grimme, S. J. Phys. Chem. C 2014, 118 (14), 7615. doi: 10.1021/jp501237c doi: 10.1021/jp501237c
29. [29]
  Smith, D. G.; Burns, L. A.; Patkowski, K.; Sherrill, C. D. J. Phys. Chem. Lett. 2016, 7 (12), 2197. doi: 10.1021/acs.jpclett.6b00780 doi: 10.1021/acs.jpclett.6b00780
30. [30]
  Li, S. S.; Jira, E. R.; Angello, N. H.; Li, J. L.; Yu, H.; Moore, J. S.; Diao, Y.; Burke, M. D.; Schroeder, C. M. Nat. Commun. 2022, 13 (1), 8. doi: 10.1038/s41467-022-29796-2 doi: 10.1038/s41467-022-29796-2
31. [31]
  Makk, P.; Tomaszewski, D.; Martinek, J.; Balogh, Z.; Csonka, S.; Wawrzyniak, M.; Frei, M.; Venkataraman, L.; Halbritter, A. ACS Nano 2012, 6 (4), 3411. doi: 10.1021/nn300440f doi: 10.1021/nn300440f
32. [32]
  Balogh, Z.; Makk, P.; Halbritter, A. Beilstein J. Nanotechnology 2015, 6, 1369. doi: 10.3762/bjnano.6.141 doi: 10.3762/bjnano.6.141
33. [33]
  Huang, C.; Jevric, M.; Borges, A.; Olsen, S. T.; Hamill, J. M.; Zheng, J. T.; Yang, Y.; Rudnev, A.; Baghernejad, M.; Broekmann, P.; et al. Nat. Commun. 2017, 8, 15436. doi: 10.1038/ncomms15436 doi: 10.1038/ncomms15436
1. [1]
  Qiaowen CHANG , Ke ZHANG , Guangying HUANG , Nuonan LI , Weiping LIU , Fuquan BAI , Caixian YAN , Yangyang FENG , Chuan ZUO . Syntheses, structures, and photo-physical properties of iridium phosphorescent complexes with phenylpyridine derivatives bearing different substituting groups. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 235-244. doi: 10.11862/CJIC.20240311
2. [2]
  Jingwen Wang , Minghao Wu , Xing Zuo , Yaofeng Yuan , Yahao Wang , Xiaoshun Zhou , Jianfeng Yan . Advances in the Application of Electrochemical Regulation in Investigating the Electron Transport Properties of Single-Molecule Junctions. University Chemistry, 2025, 40(3): 291-301. doi: 10.12461/PKU.DXHX202406023
3. [3]
  Ruonan Li , Shijie Liang , Yunhua Xu , Cuifen Zhang , Zheng Tang , Baiqiao Liu , Weiwei Li . Chlorine-Substituted Double-Cable Conjugated Polymers with Near-Infrared Absorption for Low Energy Loss Single-Component Organic Solar Cells. Acta Physico-Chimica Sinica, 2024, 40(8): 2307037-0. doi: 10.3866/PKU.WHXB202307037
4. [4]
  Yuhao SUN , Qingzhe DONG , Lei ZHAO , Xiaodan JIANG , Hailing GUO , Xianglong MENG , Yongmei GUO . Synthesis and antibacterial properties of silver-loaded sod-based zeolite. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 761-770. doi: 10.11862/CJIC.20230169
5. [5]
  Zhiwen HUANG , Qi LIU , Jianping LANG . W/Cu/S cluster-based supramolecular macrocycles and their third-order nonlinear optical responses. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 79-87. doi: 10.11862/CJIC.20240184
6. [6]
  .
  CCS Chemistry | 超分子活化底物为自由基促进高效选择性光催化氧化
  . CCS Chemistry, 2025, 7(10.31635/ccschem.025.202405229): -.
7. [7]
  Yaqin Zheng , Lian Zhuo , Meng Li , Chunying Rong . Enhancing Understanding of the Electronic Effect of Substituents on Benzene Rings Using Quantum Chemistry Calculations. University Chemistry, 2025, 40(3): 193-198. doi: 10.12461/PKU.DXHX202406119
8. [8]
  Dan Liu . 可见光-有机小分子协同催化的不对称自由基反应研究进展. University Chemistry, 2025, 40(6): 118-128. doi: 10.12461/PKU.DXHX202408101
9. [9]
  Yujie WANG , Laobang WANG , Zheng ZHANG , Qi LIU , Jianping LANG . Construction of W/Cu/S cluster-based supramolecular compounds via alkynyl/sulfur cycloaddition and their third-order nonlinear optical properties. Chinese Journal of Inorganic Chemistry, 2025, 41(10): 2069-2077. doi: 10.11862/CJIC.20250129
10. [10]
  Xinyu CHENG , Xinran CHEN , Fei LI , Chen CHEN , NevisNathaniel L. , Kai CHEN . 两例同构的七元瓜环基超分子自组装体的合成、Hirshfeld表面分析及其性质. Chinese Journal of Inorganic Chemistry, 2026, 42(8): 1637-1646. doi: 10.11862/CJIC.20260049
11. [11]
  Wenhao Zhang , Haisheng Fang , Lijuan Liu , Huaihao Tang , Chengyi Xiao , Weiwei Li . Spacer isomerization engineering in double-cable conjugated polymers for optimized molecular packing and enhanced photovoltaic performance. Acta Physico-Chimica Sinica, 2026, 42(10): 100229-0. doi: 10.1016/j.actphy.2025.100229
12. [12]
  Xinyi MA , Yuhang XIAO , Qian LI , Zihuan YAN , Chengyan LIU , Xiguang GAO , Hongju YIN , Feixiang CHENG . Thienyl metal coordination polymers: Preparation and photocatalytic degradation performance of phenol. Chinese Journal of Inorganic Chemistry, 2026, 42(5): 969-979. doi: 10.11862/CJIC.20250317
13. [13]
  Wenjuan SHI , Yuxuan LEI , Lei HOU , Yaoyu WANG . Synthesis, structure, and luminescence properties of trinucluear Cu(Ⅰ)-pyrazole complexes containing different substituent groups. Chinese Journal of Inorganic Chemistry, 2026, 42(3): 543-550. doi: 10.11862/CJIC.20250270
14. [14]
  Dan Zhou , Xinyue Liu , Zijing Guo , Jianping Yang , Zeying Guo , Zhuoer Ren , E Yu , Ting Pan , Doudou Ren , Zhicong Zeng . Development and teaching design of astigmatic displacement microscopy: a recommended experiment for chemical metrology (micro-nano advanced characterization). University Chemistry, 2026, 41(6): 196-203. doi: 10.12461/PKU.DXHX202511180
15. [15]
  Changjia Hu , Sinuo Li , Wen Jiang , Ruiyang Wu , Wenhong Ruan , Rong Lai . 分子盾牌：解锁防晒的化学密码. University Chemistry, 2026, 41(5): 14-25. doi: 10.12461/PKU.DXHX202510001
16. [16]
  Yi DING , Peiyu LIAO , Jianhua JIA , Mingliang TONG . Structure and photoluminescence modulation of silver(Ⅰ)-tetra(pyridin-4-yl)ethene metal-organic frameworks by substituted benzoates. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 141-148. doi: 10.11862/CJIC.20240393
17. [17]
  Jianchuan Wang , Wei Wu , Cunpu Li , Zhaohong Zuo , Luxi Tan . Exploration on the Construction of Polymer Course Groups in Non-Polymer-Related Majors. University Chemistry, 2026, 41(2): 154-160. doi: 10.12461/PKU.DXHX202502095
18. [18]
  Wenying Shi , Xianggui Kong , Hong Yan . Supramolecular chemistry: a molecularly functional world built by the noncovalent code. University Chemistry, 2026, 41(7): 134-143. doi: 10.12461/PKU.DXHX202506051
19. [19]
  Xiaoqi LAN , Wei LI , Long JING , Mengyu SU , Xiaoling LUO , Zheng LIU , Qun TANG . Synthesis, crystal structure, and spectral properties of transition-metal-organic frameworks based on thiophene carboxylic acid ligands. Chinese Journal of Inorganic Chemistry, 2026, 42(2): 309-316. doi: 10.11862/CJIC.20250212
20. [20]
  Feng LI , Shujuan GAO . One-step preparation and energy storage properties of MXene-doped poly(3, 4-ethylenedioxythiophene) composite electrodes. Chinese Journal of Inorganic Chemistry, 2026, 42(7): 1485-1494. doi: 10.11862/CJIC.20260019

Get Citation

PDF

XML

Metrics

PDF Downloads(14)
Abstract views(5353)
HTML views(350)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142