English

Techniques and Influencing Factors for Single Molecule Electronic Conductance Measurements

• Cheng Pengkun ,
• Li Yunchuan ,
• Chang Shuai ^,

• State Key Laboratory of Refractories and Metallurgy, Institute of Advanced Materials and Nanotechnology, Wuhan University of Science and Technology, Wuhan 430081, P. R. China

Corresponding author: Shuai Chang. Email: schang23@wust.edu.cn

• Received Date: 24 September 2019
  Accepted Date: 19 November 2019
  Revised Date: 18 November 2019
  Available Online: 15 November 2020
• Fund Project:

  The project was supported by the National Natural Science Foundation of China (21705122)

Abstract: Molecular electronics is an important field for the application of nanotechnologies with an ultimate goal of building functional devices using single molecules or molecular arrays to realize the same functionality as macroscopic devices. To attain this goal, reliable techniques for measuring and manipulating electron transfer processes through single molecules are essential. There are various techniques and many environmental factors influencing single-molecule electronic conductance measurements. In this review, we first provide a detailed introduction and classification of the current well-accepted techniques in this field for measuring single-molecule conductance. All available techniques are summarized into two categories: the fixed junction technique and break junction technique. The break junction technique involves repeatedly forming and breaking molecular junctions by mechanically controlling a pair of electrodes moving into and out of contact in the presence of target molecules. Single-molecule conductance can be determined from the conductance plateaus that appear in typical conductance decay traces when molecules bind two electrodes during their separation process. In contrast, the fixed junction technique is to fix the distance between a pair of electrodes and measure the conductance fluctuations when a single molecule binds the two electrodes stochastically. Both techniques comprise different application methods and have been employed preferentially by different groups. Specific features of both techniques and their intrinsic advantages are compared and summarized in Section 4.Next, we systematically summarize the factors affecting the molecular conductance during the course of measurements, which are the focus of the current academic community in the field. As shown in the middle of the image above, the electrode, anchoring group, and target molecule are the three key elements in constructing a single-molecule junction. The contact geometry between the molecule and the electrode and the associated coupling strength can profoundly affect the conductance characteristics of single molecules. The properties of anchoring groups can determine whether a molecule is primarily transported by electrons or holes. A good selection of electrode materials can improve the yield of single-molecule junctions and facilitate strong electronic couplings with the target molecules. The conductance characteristics of saturated and conjugated molecules are quite different due to their diverse band gaps. Moreover, various substituents can be modified onto the backbone of the molecules, which can raise or lower the energy level of the frontier orbitals of molecules to different degrees, thereby affecting the conductance properties of target molecules. In addition to these factors for the key elements, the investigated molecules can be measured in a variety of environments, including organic solvents, high vacuum, aqueous solution, ionic liquids, or the atmosphere, and the work function of the metal contact may change in different environments. The change in work function can change the gap between the electrode Fermi energy and the frontier orbital of a target molecule, influencing the measured conductance. Additionally, both the electrical field orientation and the bias values applied have a significant effect on the molecular structures and thus their conductance characteristics. Temperature can also affect the charge transport when hopping dominates the transport mechanism. Meanwhile, pH affects the interactions between H⁺/OH^- and the anchoring groups, which indirectly induces a change in the tunneling barrier.In this review, the influencing factors are comprehensively illustrated from two perspectives: internal factors (anchoring group, electrode, and target molecule) and external factors (voltage, temperature, solvent, pH value, and others). In addition, new approaches for modulating the molecular conductance (modulation of energy levels, light or heat stimulation, and others) that have been developed in recent years are reviewed, and investigations of chemical reactions at the single-molecule level using these methods are highlighted. Finally, the potential applications of these techniques and correlated modulating approaches are summarized and a prospective is provided for the field of single-molecule electronics.

Key words:
• Single molecule conductance measurement
•  /  Fixed junction
•  /  Break junction
•  /  Anchoring group
•  /  Influencing factor of conductance

• 1. [1]

     Feynman, R. P. Calif. Inst. Technol. J. Eng. Sci. 1960, 4, 23.
     

  2. [2]

     Aviram, A.; Ratner, M. A. Chem. Phys. Lett. 1974, 29, 277. doi: 10.1016/0009-2614(74)85031-1 doi: 10.1016/0009-2614(74)85031-1
     

  3. [3]

     Qin, L.; Park, S.; Huang, L.; Mirkin, C. A. Science 2005, 309, 113. doi: 10.1126/science.1112666 doi: 10.1126/science.1112666
     

  4. [4]

     Chen, X.; Yeganeh, S.; Qin, L.; Li, S.; Xue, C.; Braunschweig, A. B.; Schatz, G. C.; Ratner, M. A.; Mirkin, C. A. Nano Lett. 2009, 9, 3974. doi: 10.1021/nl9018726 doi: 10.1021/nl9018726
     

  5. [5]

     Klein, D. L.; McEuen, P. L.; Katari, J. E. B.; Roth, R.; Alivisatos, A. P. Appl. Phys. Lett. 1996, 68, 2574. doi: 10.1063/1.116188 doi: 10.1063/1.116188
     

  6. [6]

     Park, H.; Lim, A. K. L.; Alivisatos, A. P. Appl. Phys. Lett. 1999, 75, 301. doi: 10.1063/1.124354 doi: 10.1063/1.124354
     

  7. [7]

     Reed, M. A.; Zhou, C.; Muller, C. J.; Burgin, T. P.; Tour, J. M. Science 1997, 278, 252. doi: 10.1126/science.278.5336.252 doi: 10.1126/science.278.5336.252
     

  8. [8]

     Zhang, Y. P.; Chen, L. C.; Zhang, Z. Q.; Cao, J. J.; Tang, C.; Liu, J.; Duan, L. L.; Huo, Y.; Shao, X.; Hong, W.; et al. J. Am. Chem. Soc. 2018, 140, 6531. doi: 10.1021/jacs.8b02825 doi: 10.1021/jacs.8b02825
     

  9. [9]

     Wold, D. J.; Frisbie, C. D. J. Am. Chem. Soc. 2000, 122, 2970. doi: 10.1021/ja994468h doi: 10.1021/ja994468h
     

  10. [10]

      Cui, X. D.; Primak, A.; Zarate, X.; Tomfohr, J.; Sankey, O. F.; Moore, A. L.; Moore, T. A.; Gust, D.; Harris, G.; Lindsay, S. M. Science 2001, 294, 571. doi: 10.1126/science.1064354 doi: 10.1126/science.1064354
      

  11. [11]

      Xu, B.; Xiao, X.; Tao, N. J. J. Am. Chem. Soc. 2003, 125, 16164. doi: 10.1021/ja038949j doi: 10.1021/ja038949j
      

  12. [12]

      Xu, B.; Tao, N. J. Science 2003, 301, 1221. doi: 10.1126/science.1087481 doi: 10.1126/science.1087481
      

  13. [13]

      He, J.; Sankey, O.; Lee, M.; Tao, N.; Li, X.; Lindsay, S. Faraday Discuss. 2006, 131, 145. doi: 10.1039/b508434m doi: 10.1039/b508434m
      

  14. [14]

      Haiss, W.; Nichols, R. J.; van Zalinge, H.; Higgins, S. J.; Bethell, D.; Schiffrin, D. J. Phys. Chem. Chem. Phys. 2004, 6, 4330. doi: 10.1039/B404929B doi: 10.1039/B404929B
      

  15. [15]

      Pla-Vilanova, P.; Aragones, A. C.; Ciampi, S.; Sanz, F.; Darwish, N.; Diez-Perez, I. Nanotechnology 2015, 26, 381001. doi: 10.1088/0957-4484/26/38/381001 doi: 10.1088/0957-4484/26/38/381001
      

  16. [16]

      Haiss, W.; van Zalinge, H.; Higgins, S. J.; Bethell, D.; Höbenreich, H.; Schiffrin, D. J.; Nichols, R. J. J. Am. Chem. Soc. 2003, 125, 15294. doi: 10.1021/ja038214e doi: 10.1021/ja038214e
      

  17. [17]

      Haiss, W.; Wang, C.; Grace, I.; Batsanov, A. S.; Schiffrin, D. J.; Higgins, S. J.; Bryce, M. R.; Lambert, C. J.; Nichols, R. J. Nat. Mater. 2006, 5 (12), 995. doi: 10.1038/nmat1781 doi: 10.1038/nmat1781
      

  18. [18]

      Liang, X.; Chou, S. Y. Nano Lett. 2008, 8, 1472. doi: 10.1021/nl080473k doi: 10.1021/nl080473k
      

  19. [19]

      Guo, X.; Small, J. P.; Klare, J. E.; Wang, Y.; Purewal, M. S.; Tam, I. W.; Hong, B. H.; Caldwell, R.; Huang, L.; O'Brien, S. Science 2006, 311, 356. doi: 10.1126/science.1120986 doi: 10.1126/science.1120986
      

  20. [20]

      Prins, F.; Barreiro, A.; Ruitenberg, J. W.; Seldenthuis, J. S.; Aliaga-Alcalde, N.; Vandersypen, L. M. K.; van der Zant, H. S. J. Nano Lett. 2011, 11, 4607. doi: 10.1021/nl202065x doi: 10.1021/nl202065x
      

  21. [21]

      Brandl, T.; El Abbassi, M.; Stefani, D.; Frisenda, R.; Harzmann, G. D.; van der Zant, H. S. J.; Mayor, M. Eur. J. Org. Chem. 2019, 2019, 5334. doi: 10.1002/ejoc.201900432 doi: 10.1002/ejoc.201900432
      

  22. [22]

      Lumbroso, O. S.; Simine, L.; Nitzan, A.; Segal, D.; Tal, O. Nature 2018, 562, 240. doi: 10.1038/s41586-018-0592-2 doi: 10.1038/s41586-018-0592-2
      

  23. [23]

      Su, T. A.; Neupane, M.; Steigerwald, M. L.; Venkataraman, L.; Nuckolls, C. Nat. Rev. Mater. 2016, 1, 2058. doi: 10.1038/natrevmats.2016.2 doi: 10.1038/natrevmats.2016.2
      

  24. [24]

      Xiang, D.; Wang, X.; Jia, C.; Lee, T.; Guo, X. Chem. Rev. 2016, 116, 4318. doi: 10.1021/acs.chemrev.5b00680 doi: 10.1021/acs.chemrev.5b00680
      

  25. [25]

      余培锴, 冯安妮, 赵世强, 魏珺颖, 杨扬, 师佳, 洪文晶.物理化学学报, 2019, 35, 829. doi: 10.3866/PKU.WHXB201811027Yu, P.; Feng, A.; Zhao, S.; Wei, J.; Yang, Y.; Shi, J.; Hong, W. Acta Phys. -Chim. Sin. 2019, 35 829. doi: 10.3866/PKU.WHXB201811027
      

  26. [26]

      Muller, C. J.; van Ruitenbeek, J. M.; de Jongh, L. J. Phys. Rev. Lett. 1992, 69, 140. doi: 10.1103/PhysRevLett.69.140 doi: 10.1103/PhysRevLett.69.140
      

  27. [27]

      Huang, C.; Rudnev, A. V.; Hong, W.; Wandlowski, T. Chem. Soc. Rev. 2015, 44, 889. doi: 10.1039/c4cs00242c doi: 10.1039/c4cs00242c
      

  28. [28]

      Konishi, T.; Kiguchi, M.; Takase, M.; Nagasawa, F.; Nabika, H.; Ikeda, K.; Uosaki, K.; Ueno, K.; Misawa, H.; Murakoshi, K. J. Am. Chem. Soc. 2013, 135, 1009. doi: 10.1021/ja307821u doi: 10.1021/ja307821u
      

  29. [29]

      Xiang, D.; Jeong, H.; Lee, T.; Mayer, D. Adv. Mater. 2013, 25, 4845. doi: 10.1002/adma.201301589 doi: 10.1002/adma.201301589
      

  30. [30]

      Wang, L.; Wang, L.; Zhang, L.; Xiang, D. Top. Curr. Chem. (Cham) 2017, 375, 61. doi: 10.1007/s41061-017-0149-0 doi: 10.1007/s41061-017-0149-0
      

  31. [31]

      Venkataraman, L.; Klare, J. E.; Tam, I. W.; Nuckolls, C.; Hybertsen, M. S.; Steigerwarld, M. L. Nano Lett. 2006, 6, 458. doi: 10.1021/nl052373+ doi: 10.1021/nl052373+
      

  32. [32]

      Park, Y. S.; Whalley, A. C.; Kamenetska, M.; Steigerwald, M. L.; Hybertsen, M. S.; Nuckolls, C.; Venkataraman, L. J. Am. Chem. Soc. 2007, 129, 15768. doi: 10.1021/ja0773857 doi: 10.1021/ja0773857
      

  33. [33]

      Hong, W.; Li, H.; Liu, S. X.; Fu, Y.; Li, J.; Kaliginedi, V.; Decurtins, S.; Wandlowski, T. J. Am. Chem. Soc. 2012, 134, 19425. doi: 10.1021/ja307544w doi: 10.1021/ja307544w
      

  34. [34]

      Hong, W.; Manrique, D. Z.; Moreno-Garcia, P.; Gulcur, M.; Mishchenko, A.; Lambert, C. J.; Bryce, M. R.; Wandlowski, T. J. Am. Chem. Soc. 2012, 134, 2292. doi: 10.1021/ja209844r doi: 10.1021/ja209844r
      

  35. [35]

      Li, Z.; Smeu, M.; Ratner, M. A.; Borguet, E. J. Phys. Chem. C 2013, 117, 14890. doi: 10.1021/jp309871d doi: 10.1021/jp309871d
      

  36. [36]

      Ponce, J.; Arroyo, C. R.; Tatay, S.; Frisenda, R.; Gavina, P.; Aravena, D.; Ruiz, E.; van der Zant, H. S.; Coronado, E. J. Am. Chem. Soc. 2014, 136, 8314. doi: 10.1021/ja5012417 doi: 10.1021/ja5012417
      

  37. [37]

      Xiao, B.; Liang, F.; Liu, S.; Im, J.; Li, Y.; Liu, J.; Zhang, B.; Zhou, J.; He, J.; Chang, S. Nanotechnology 2018, 29, 365501. doi: 10.1088/1361-6528/aacb63 doi: 10.1088/1361-6528/aacb63
      

  38. [38]

      Chen, F.; Li, X.; Hihath, J.; Huang, Z.; Tao, N. J. Am. Chem. Soc. 2006, 128, 15874. doi: 10.1021/ja065864k doi: 10.1021/ja065864k
      

  39. [39]

      Quek, S. Y.; Venkataraman, L.; Choi, H. J.; Louie, S. G.; Hybertsen, M. S.; Neaton, J. B. Nano Lett. 2007, 7, 3477. doi: 10.1021/nl072058i doi: 10.1021/nl072058i
      

  40. [40]

      Dell'Angela, M.; Kladnik, G.; Cossaro, A.; Verdini, A.; Kamenetska, M.; Tamblyn, I.; Quek, S. Y.; Neaton, J. B.; Cvetko, D.; Morgante, A. Nano Lett. 2010, 10, 2470. doi: 10.1021/nl100817h doi: 10.1021/nl100817h
      

  41. [41]

      Venkataraman, L.; Park, Y. S.; Whalley, A. C.; Nuckolls, C.; Hybertsen, M. S.; Steigerwald, M. L. Nano Lett. 2007, 7, 502. doi: 10.1021/nl062923j doi: 10.1021/nl062923j
      

  42. [42]

      Mishchenko, A.; Zotti, L. A.; Vonlanthen, D.; Bürkle, M.; Pauly, F.; Cuevas, J. C.; Mayor, M.; Wandlowski, T. J. Am. Chem. Soc. 2011, 133, 184. doi: 10.1021/ja107340t doi: 10.1021/ja107340t
      

  43. [43]

      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, 230. doi: 10.1038/nnano.2009.10 doi: 10.1038/nnano.2009.10
      

  44. [44]

      Dadosh, T.; Gordin, Y.; Krahne, R.; Khivrich, I.; Mahalu, D.; Frydman, V.; Sperling, J.; Yacoby, A.; Bar-Joseph, I. Nature 2005, 436, 677. doi: 10.1038/nature03898 doi: 10.1038/nature03898
      

  45. [45]

      Martin, C. A.; Ding, D.; Sorensen, J. K.; Bjornholm, T.; van Ruitenbeek, J. M.; van der Zant, H. S. J. Am. Chem. Soc. 2008, 130, 13198. doi: 10.1021/ja804699a doi: 10.1021/ja804699a
      

  46. [46]

      Schneebeli, S. T.; Kamenetska, M.; Cheng, Z.; Skouta, R.; Friesner, R. A.; Venkataraman, L.; Breslow, R. J. Am. Chem. Soc. 2011, 133, 2136. doi: 10.1021/ja111320n doi: 10.1021/ja111320n
      

  47. [47]

      Kiguchi, M.; Tal, O.; Wohlthat, S.; Pauly, F.; Krieger, M.; Djukic, D.; Cuevas, J. C.; van Ruitenbeek, J. M. Phys. Rev. Lett. 2008, 101, 046801. doi: 10.1103/PhysRevLett.101.046801 doi: 10.1103/PhysRevLett.101.046801
      

  48. [48]

      Kaneko, S.; Nakazumi, T.; Kiguchi, M. J. Phys. Chem. Lett. 2010, 1, 3520. doi: 10.1021/jz101506u doi: 10.1021/jz101506u
      

  49. [49]

      Li, Y.; Xiao, B.; Chen, R.; Chen, H.; Dong, J.; Liu, Y.; Chang, S. Chem. Commun. 2019, 55, 8325. doi: 10.1039/c9cc02998b doi: 10.1039/c9cc02998b
      

  50. [50]

      Cheng, Z. L.; Skouta, R.; Vazquez, H.; Widawsky, J. R.; Schneebeli, S.; Chen, W.; Hybertsen, M. S.; Breslow, R.; Venkataraman, L. Nat. Nanotechnol. 2011, 6, 353. doi: 10.1038/nnano.2011.66 doi: 10.1038/nnano.2011.66
      

  51. [51]

      Chen, W.; Widawsky, J. R.; Vazquez, H.; Schneebeli, S. T.; Hybertsen, M. S.; Breslow, R.; Venkataraman, L. J. Am. Chem. Soc. 2011, 133, 17160. doi: 10.1021/ja208020j doi: 10.1021/ja208020j
      

  52. [52]

      Hines, T.; Diez-Perez, I.; Nakamura, H.; Shimazaki, T.; Asai, Y.; Tao, N. J. Am. Chem. Soc. 2013, 135, 3319. doi: 10.1021/ja3106434 doi: 10.1021/ja3106434
      

  53. [53]

      Ko, C. H.; Huang, M. J.; Fu, M. D.; Chen, C. H. J. Am. Chem. Soc. 2010, 132, 756. doi: 10.1021/ja9084012 doi: 10.1021/ja9084012
      

  54. [54]

      Zhou, X. S.; Liang, J. H.; Chen, Z. B.; Mao, B. W. Electrochem. Commun. 2011, 13, 407. doi: 10.1016/j.elecom.2011.02.005 doi: 10.1016/j.elecom.2011.02.005
      

  55. [55]

      Peng, Z. L.; Chen, Z. B.; Zhou, X. Y.; Sun, Y. Y.; Liang, J. H.; Niu, Z. J.; Zhou, X. S.; Mao, B. W. J. Phys. Chem. C 2012, 116, 21699. doi: 10.1021/jp3069046 doi: 10.1021/jp3069046
      

  56. [56]

      Wang, Y. H.; Zhou, X. Y.; Sun, Y. Y.; Han, D.; Zheng, J. F.; Niu, Z. J.; Zhou, X. S. Electrochim. Acta 2014, 123, 205. doi: 10.1016/j.electacta.2014.01.041 doi: 10.1016/j.electacta.2014.01.041
      

  57. [57]

      He, C.; Zhang, Q.; Fan, Y.; Zhao, C.; Zhao, C.; Ye, J.; Dappe, Y.; Nichols, R.; Yang, L. ChemPhysChem 2019, 20, 1830. doi: 10.1002/cphc.201900424 doi: 10.1002/cphc.201900424
      

  58. [58]

      Zhou, X. S.; Wei, Y. M.; Liu, L.; Chen, Z. B.; Tang, J.; Mao, B. W. J. Am. Chem. Soc. 2008, 130, 13228. doi: 10.1021/ja8055276 doi: 10.1021/ja8055276
      

  59. [59]

      Zhou, C.; Li, X.; Gong, Z.; Jia, C.; Lin, Y.; Gu, C.; He, G.; Zhong, Y.; Yang, J.; Guo, X. Nat. Commun. 2018, 9, 807. doi: 10.1038/s41467-018-03203-1 doi: 10.1038/s41467-018-03203-1
      

  60. [60]

      Gu, C.; Hu, C.; Wei, Y.; Lin, D.; Jia, C.; Li, M.; Su, D.; Guan, J.; Xia, A.; Xie, L. Nano Lett. 2018, 18, 4156. doi: 10.1021/acs.nanolett.8b00949 doi: 10.1021/acs.nanolett.8b00949
      

  61. [61]

      Sarwat, S. G.; Gehring, P.; Rodriguez Hernandez, G.; Warner, J. H.; Briggs, G. A. D.; Mol, J. A.; Bhaskaran, H. Nano Lett. 2017, 17, 3688. doi: 10.1021/acs.nanolett.7b00909 doi: 10.1021/acs.nanolett.7b00909
      

  62. [62]

      Bellunato, A.; Vrbica, S. D.; Sabater, C.; de Vos, E. W.; Fermin, R.; Kanneworff, K. N.; Galli, F.; van Ruitenbeek, J. M.; Schneider, G. F. Nano Lett. 2018, 18, 2505. doi: 10.1021/acs.nanolett.8b00171 doi: 10.1021/acs.nanolett.8b00171
      

  63. [63]

      Peiris, C. R.; Vogel, Y.; Le Brun, A. P. C.; Aragonès, A.; Coote, M. L.; Díez-Pérez, I.; Ciampi, S.; Darwish, N. J. Am. Chem. Soc. 2019, 141, 14788. doi: 10.1021/jacs.9b07125 doi: 10.1021/jacs.9b07125
      

  64. [64]

      Caneva, S.; Gehring, P.; Garcia-Suarez, V. M.; Garcia-Fuente, A.; Stefani, D.; Olavarria-Contreras, I. J.; Ferrer, J.; Dekker, C.; van der Zant, H. S. J. Nat. Nanotechnol. 2018, 13, 1126. doi: 10.1038/s41565-018-0258-0 doi: 10.1038/s41565-018-0258-0
      

  65. [65]

      Xiang, L.; Hines, T.; Palma, J. L.; Lu, X.; Mujica, V.; Ratner, M. A.; Zhou, G.; Tao, N. J. Am. Chem. Soc. 2016, 138, 679. doi: 10.1021/jacs.5b11605 doi: 10.1021/jacs.5b11605
      

  66. [66]

      Nitzan, A. Annu. Rev. Phys. Chem. 2001, 52, 681. doi: 10.1146/annurev.physchem.52.1.681 doi: 10.1146/annurev.physchem.52.1.681
      

  67. [67]

      Nitzan, A. J. Phys. Chem. A 2001, 105, 2677. doi: 10.1021/jp003884h doi: 10.1021/jp003884h
      

  68. [68]

      Ie, Y.; Okamoto, Y.; Inoue, T.; Tone, S.; Seo, T.; Honda, Y.; Tanaka, S.; Lee, S. K.; Ohto, T.; Yamada, R. J. Phys. Chem. Lett. 2019, 10, 3197. doi: 10.1021/acs.jpclett.9b00747 doi: 10.1021/acs.jpclett.9b00747
      

  69. [69]

      Yasini, P.; Afsari, S.; Peng, H.; Pikma, P.; Perdew, J. P.; Borguet, E. J. Am. Chem. Soc. 2019, 141, 10109. doi: 10.1021/jacs.9b05448 doi: 10.1021/jacs.9b05448
      

  70. [70]

      Stuyver, T.; Fias, S.; Geerlings, P.; De Proft, F.; Alonso, M. J. Phys. Chem. C 2018, 122, 19842. doi: 10.1021/acs.jpcc.8b01424 doi: 10.1021/acs.jpcc.8b01424
      

  71. [71]

      Ramos-Berdullas, N.; Graña, A. M.; Mandado, M. Theor. Chem. Acc. 2015, 134. doi: 10.1007/s00214-015-1620-z doi: 10.1007/s00214-015-1620-z
      

  72. [72]

      Ramos-Berdullas, N.; Mandado, M. Chemistry 2013, 19, 3646. doi: 10.1002/chem.201203324 doi: 10.1002/chem.201203324
      

  73. [73]

      Chen, W.; Li, H.; Widawsky, J. R.; Appayee, C.; Venkataraman, L.; Breslow, R. J. Am. Chem. Soc. 2014, 136, 918. doi: 10.1021/ja411143s doi: 10.1021/ja411143s
      

  74. [74]

      Mahendran, A.; Gopinath, P.; Breslow, R. Tetrahedron Lett. 2015, 56, 4833. doi: 10.1016/j.tetlet.2015.06.076 doi: 10.1016/j.tetlet.2015.06.076
      

  75. [75]

      Stuyver, T.; Perrin, M. L.; Geerlings, P.; Proft, F. D.; Alonso, M. J. Am. Chem. Soc. 2018, 140, 1313. doi: 10.1021/jacs.7b09464 doi: 10.1021/jacs.7b09464
      

  76. [76]

      Gil-Guerrero, S.; Ramos-Berdullas, N.; Mandado, M. Org. Electron. 2018, 61, 177. doi: 10.1016/j.orgel.2018.05.043 doi: 10.1016/j.orgel.2018.05.043
      

  77. [77]

      Zhang, G. P.; Xie, Z.; Song, Y.; Wei, M. Z.; Hu, G. C.; Wang, C. K. Org. Electron. 2017, 48, 29. doi: 10.1016/j.orgel.2017.05.032 doi: 10.1016/j.orgel.2017.05.032
      

  78. [78]

      Liu, J.; Zhao, X.; Al-Galiby, Q.; Huang, X.; Zheng, J.; Li, R.; Huang, C.; Yang, Y.; Shi, J.; Manrique, D. Z. Angew. Chem. Int. Ed. 2017, 56, 13061. doi: 10.1002/anie.201707710 doi: 10.1002/anie.201707710
      

  79. [79]

      华煜晖, 张弘, 夏海平.有机化学, 2018, 38, 11. doi: 10.6023/cjoc201709009Hua, Y.; Zhang, H.; Xia, H. Chin. J. Org. Chem. 2018, 38, 11. doi: 10.6023/cjoc201709009
      

  80. [80]

      Pauly, F.; Viljas, J. K.; Cuevas, J. C.; Schön, G. Phys. Rev. B 2008, 77, 155312. doi: 10.1103/PhysRevB.77.155312 doi: 10.1103/PhysRevB.77.155312
      

  81. [81]

      Huang, B.; Liu, X.; Yuan, Y.; Hong, Z. W.; Zheng, J. F.; Pei, L. Q.; Shao, Y.; Li, J. F.; Zhou, X. S.; Chen, J. J. Am. Chem. Soc. 2018, 140, 17685. doi: 10.1021/jacs.8b10450 doi: 10.1021/jacs.8b10450
      

  82. [82]

      Li, Y.; Buerkle, M.; Li, G.; Rostamian, A.; Wang, H.; Wang, Z.; Bowler, D. R.; Miyazaki, T.; Xiang, L.; Asai, Y. Nat. Mater. 2019, 18, 357. doi: 10.1038/s41563-018-0280-5 doi: 10.1038/s41563-018-0280-5
      

  83. [83]

      Quinn, J. R.; Foss, F. W.; Venkataraman, L.; Hybertsen, M. S.; Breslow, R. J. Am. Chem. Soc. 2007, 129, 6714. doi: 10.1021/ja0715804 doi: 10.1021/ja0715804
      

  84. [84]

      Venkataraman, L.; Klare, J. E.; Nuckolls, C.; Hybertsen, M. S.; Steigerwald, M. L. Nature 2006, 442, 904. doi: 10.1038/nature05037 doi: 10.1038/nature05037
      

  85. [85]

      Huang, J. R.; Huang, H.; Tao, C. P.; Zheng, J. F.; Yuan, Y.; Hong, Z. W.; Shao, Y.; Niu, Z. J.; Chen, J. Z.; Zhou, X. S. Nanoscale Res. Lett. 2019, 14, 253. doi: 10.1186/s11671-019-3087-7 doi: 10.1186/s11671-019-3087-7
      

  86. [86]

      Chen, Z.; Chen, L.; Liu, J.; Li, R.; Tang, C.; Hua, Y.; Chen, L.; Shi, J.; Yang, Y.; Liu, J. J. Phys. Chem. Lett. 2019, 10, 3453. doi: 10.1021/acs.jpclett.9b00796 doi: 10.1021/acs.jpclett.9b00796
      

  87. [87]

      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, 1472. doi: 10.1021/acs.jpcc.6b10925 doi: 10.1021/acs.jpcc.6b10925
      

  88. [88]

      Zhen, S.; Mao, J. C.; Chen, L.; Ding, S.; Luo, W.; Zhou, X. S.; Qin, A.; Zhao, Z.; Tang, B. Z. Nano Lett. 2018, 18, 4200. doi: 10.1021/acs.nanolett.8b01082 doi: 10.1021/acs.nanolett.8b01082
      

  89. [89]

      Yang, G.; Wu, H.; Wei, J.; Zheng, J.; Chen, Z.; Liu, J.; Shi, J.; Yang, Y.; Hong, W. Chin. Chem. Lett. 2018, 29, 147. doi: 10.1016/j.cclet.2017.06.015 doi: 10.1016/j.cclet.2017.06.015
      

  90. [90]

      Li, H.; Garner, M. H.; Shangguan, Z.; Zheng, Q.; Su, T. A.; Neupane, M.; Li, P.; Velian, A.; Steigerwald, M. L.; Xiao, S. Chem. Sci. 2016, 7, 5657. doi: 10.1039/c6sc01360k doi: 10.1039/c6sc01360k
      

  91. [91]

      Garner, M. H.; Li, H.; Chen, Y.; Su, T. A.; Shangguan, Z.; Paley, D. W.; Liu, T.; Ng, F.; Li, H.; Xiao, S. Nature 2018, 558, 415. doi: 10.1038/s41586-018-0197-9 doi: 10.1038/s41586-018-0197-9
      

  92. [92]

      Widawsky, J. R.; Kamenetska, M.; Klare, J.; Nuckolls, C.; Steigerwald, M. L.; Hybertsen, M. S.; Venkataraman, L. Nanotechnology 2009, 20, 434009. doi: 10.1088/0957-4484/20/43/434009 doi: 10.1088/0957-4484/20/43/434009
      

  93. [93]

      Guo, S.; Hihath, J.; Diez-Perez, I.; Tao, N. J. Am. Chem. Soc. 2011, 133, 19189. doi: 10.1021/ja2076857 doi: 10.1021/ja2076857
      

  94. [94]

      Isshiki, Y.; Fujii, S.; Nishino, T.; Kiguchi, M. J. Am. Chem. Soc. 2018, 140, 3760. doi: 10.1021/jacs.7b13694 doi: 10.1021/jacs.7b13694
      

  95. [95]

      Aragones, A. C.; Haworth, N. L.; Darwish, N.; Ciampi, S.; Bloomfield, N. J.; Wallace, G. G.; Diez-Perez, I.; Coote, M. L. Nature 2016, 531, 88. doi: 10.1038/nature16989 doi: 10.1038/nature16989
      

  96. [96]

      Zhang, L.; Laborda, E.; Darwish, N.; Noble, B. B.; Tyrell, J. H.; Pluczyk, S.; Le Brun, A. P.; Wallace, G. G.; Gonzalez, J.; Coote, M. L. J. Am. Chem. Soc. 2018, 140, 766. doi: 10.1021/jacs.7b11628 doi: 10.1021/jacs.7b11628
      

  97. [97]

      Li, X.; Hihath, J.; Chen, F.; Masuda, T.; Zang, L.; Tao, N. J. Am. Chem. Soc. 2007, 129, 11535. doi: 10.1021/ja072990v doi: 10.1021/ja072990v
      

  98. [98]

      Darwish, N.; Diez-Perez, I.; Da Silva, P.; Tao, N.; Gooding, J. J.; Paddon-Row, M. N. Angew. Chem. Int. Ed. 2012, 51, 3203. doi: 10.1002/anie.201107765 doi: 10.1002/anie.201107765
      

  99. [99]

      Osorio, E. A.; Bjornholm, T.; Lehn, J. M.; Ruben, M.; van der Zant, H. S. J. Phys. Condens. Matter 2008, 20, 374121. doi: 10.1088/0953-8984/20/37/374121 doi: 10.1088/0953-8984/20/37/374121
      

  100. [100]

       Brooke, R. J.; Szumski, D. S.; Vezzoli, A.; Higgins, S. J.; Nichols, R. J.; Schwarzacher, W. Nano Lett. 2018, 18, 1317. doi: 10.1021/acs.nanolett.7b04995 doi: 10.1021/acs.nanolett.7b04995
       

  101. [101]

       杨扬, 刘俊扬, 晏润文, 吴德印, 田中群.高等学校化学学报, 2015, 36, 9. doi: 10.7503/cjcu20140941Yang, Y.; Liu, J.; Yan, R.; Wu, D.; Tian, Z. Chem. J. Chin. Univ. 2015, 36, 9. doi: 10.7503/cjcu20140941
       

  102. [102]

       Lee, T.; Wang, W.; Reed, M. A. Ann. New York Acad. Sci. 2003, 1006, 21. doi: 10.1196/annals.1292.001 doi: 10.1196/annals.1292.001
       

  103. [103]

       Esposito, T.; Dinolfo, P. H.; Lewis, K. M. Org. Electron. 2018, 63, 58. doi: 10.1016/j.orgel.2018.08.040 doi: 10.1016/j.orgel.2018.08.040
       

  104. [104]

       Selzer, Y.; Cabassi, M. A.; Mayer, T. S.; Allara, D. L. Nanotechnology 2004, 15, S483. doi: 10.1088/0957-4484/15/7/057 doi: 10.1088/0957-4484/15/7/057
       

  105. [105]

       Selzer, Y.; Cabassi, M. A.; Mayer, T. S.; Allara, D. L. J. Am. Chem. Soc. 2004, 126, 4052. doi: 10.1021/ja039015y doi: 10.1021/ja039015y
       

  106. [106]

       Taniguchi, M.; Morimoto, K.; Tsutsui, M.; Kawai, T. Chem. Lett. 2008, 37, 990. doi: 10.1246/cl.2008.990 doi: 10.1246/cl.2008.990
       

  107. [107]

       Leary, E.; Höbenreich, H.; Higgins, S. J.; van Zalinge, H.; Haiss, W.; Nichols, R. J.; Finch, C. M.; Grace, I.; Lambert, C. J.; McGrath, R. Phys. Rev. Lett. 2009, 102, 086801. doi: 10.1103/PhysRevLett.102.086801 doi: 10.1103/PhysRevLett.102.086801
       

  108. [108]

       Fatemi, V.; Kamenetska, M.; Neaton, J. B.; Venkataraman, L. Nano Lett. 2011, 11, 1988. doi: 10.1021/nl200324e doi: 10.1021/nl200324e
       

  109. [109]

       Milan, D. C.; Al-Owaedi, O. A.; Oerthel, M. C.; Marqués-González, S.; Brooke, R. J.; Bryce, M. R.; Cea, P.; Ferrer, J.; Higgins, S. J.; Lambert, C. J. J. Phys. Chem. C 2015, 120, 15666. doi: 10.1021/acs.jpcc.5b08877 doi: 10.1021/acs.jpcc.5b08877
       

  110. [110]

       Gunasekaran, S.; Hernangomez-Perez, D.; Davydenko, I.; Marder, S.; Evers, F.; Venkataraman, L. Nano Lett. 2018, 18, 6387. doi: 10.1021/acs.nanolett.8b02743 doi: 10.1021/acs.nanolett.8b02743
       

  111. [111]

       Liu, X.; Sangtarash, S.; Reber, D.; Zhang, D.; Sadeghi, H.; Shi, J.; Xiao, Z. Y.; Hong, W.; Lambert, C. J.; Liu, S. X. Angew. Chem. Int. Ed. 2017, 56, 173. doi: 10.1002/anie.201609051 doi: 10.1002/anie.201609051
       

  112. [112]

       Xiao, X.; Xu, B.; Tao, N. J. Am. Chem. Soc. 2004, 126, 5370. doi: 10.1021/ja049469a doi: 10.1021/ja049469a
       

  113. [113]

       Scullion, L.; Doneux, T.; Bouffier, L.; Fernig, D. G.; Higgins, S. J.; Bethell, D.; Nichols, R. J. J. Phys. Chem. C 2011, 115, 8361. doi: 10.1021/jp201222b doi: 10.1021/jp201222b
       

  114. [114]

       Yang, G.; Sangtarash, S.; Liu, Z.; Li, X.; Sadeghi, H.; Tan, Z.; Li, R.; Zheng, J.; Dong, X.; Liu, J. Chem. Sci. 2017, 8, 7505. doi: 10.1039/c7sc01014a doi: 10.1039/c7sc01014a
       

  115. [115]

       Roldan, D.; Kaliginedi, V.; Cobo, S.; Kolivoska, V.; Bucher, C.; Hong, W.; Royal, G.; Wandlowski, T. J. Am. Chem. Soc. 2013, 135, 5974. doi: 10.1021/ja401484j doi: 10.1021/ja401484j
       

  116. [116]

       van der Molen, S. J.; Liao, J.; Kudernac, T.; Agustsson, J. S.; Bernard, L.; Calame, M.; van Wees, B. J.; Feringa, B. L.; Schönenberger, C. Nano Lett. 2009, 9, 76. doi: 10.1021/nl802487j doi: 10.1021/nl802487j
       

  117. [117]

       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
       

  118. [118]

       Leary, E.; Limburg, B.; Alanazy, A.; Sangtarash, S.; Grace, I.; Swada, K.; Esdaile, L. J.; Noori, M.; Gonzalez, M. T.; Rubio-Bollinger, G. J. Am. Chem. Soc. 2018, 140, 12877. doi: 10.1021/jacs.8b06338 doi: 10.1021/jacs.8b06338
       

  119. [119]

       Li, J. J.; Bai, M. L.; Chen, Z. B.; Zhou, X. S.; Shi, Z.; Zhang, M.; Ding, S. Y.; Hou, S. M.; Schwarzacher, W.; Nichols, R. J.; et al. J. Am. Chem. Soc. 2015, 137, 5923. doi: 10.1021/ja512483y doi: 10.1021/ja512483y
       

  120. [120]

       Aragones, A. C.; Aravena, D.; Cerda, J. I.; Acis-Castillo, Z.; Li, H.; Real, J. A.; Sanz, F.; Hihath, J.; Ruiz, E.; Diez-Perez, I. Nano Lett. 2016, 16, 218. doi: 10.1021/acs.nanolett.5b03571 doi: 10.1021/acs.nanolett.5b03571
       

  121. [121]

       Iwane, M.; Fujii, S.; Nishino, T.; Kiguchi, M. J. Phys. Chem. C 2016, 120, 8936. doi: 10.1021/acs.jpcc.5b12728 doi: 10.1021/acs.jpcc.5b12728
       

  122. [122]

       Kiguchi, M.; Ohto, T.; Fujii, S.; Sugiyasu, K.; Nakajima, S.; Takeuchi, M.; Nakamura, H. J. Am. Chem. Soc. 2014, 136, 7327. doi: 10.1021/ja413104g doi: 10.1021/ja413104g
       

  123. [123]

       Leary, E.; Roche, C.; Jiang, H. W.; Grace, I.; Gonzalez, M. T.; Rubio-Bollinger, G.; Romero-Muniz, C.; Xiong, Y.; Al-Galiby, Q.; Noori, M. J. Am. Chem. Soc. 2018, 140, 710. doi: 10.1021/jacs.7b10542 doi: 10.1021/jacs.7b10542
       

  124. [124]

       Nichols, R. J.; Higgins, S. J. Acc. Chem. Res. 2016, 49, 2640. doi: 10.1021/acs.accounts.6b00373 doi: 10.1021/acs.accounts.6b00373
       

  125. [125]

       Liu, J.; Huang, X.; Wang, F.; Hong, W. Acc. Chem. Res. 2019, 52, 151. doi: 10.1021/acs.accounts.8b00429 doi: 10.1021/acs.accounts.8b00429
       

  126. [126]

       Chen, L.; Feng, A.; Wang, M.; Liu, J.; Hong, W.; Guo, X.; Xiang, D. Sci. China Chem. 2018, 61, 1368. doi: 10.1007/s11426-018-9356-2 doi: 10.1007/s11426-018-9356-2
       

  127. [127]

       顾春晖, 郭雪峰.物理化学学报, 2017, 33, 1927 doi: 10.3866/PKU.WHXB201706144Gu, C.; Guo, X. Acta Phys. -Chim. Sin. 2017, 33, 1927. doi: 10.3866/PKU.WHXB201706144
       

  128. [128]

       Šebera, J.; Lindner, M.; Gasior, J.; Mészáros, G.; Fuhr, O.; Mayor, M.; Valášek, M.; Kolivoška, V.; Hromadová, M. Nanoscale 2019, 11, 12959. doi: 10.1039/c9nr04071d doi: 10.1039/c9nr04071d
       

  129. [129]

       Zhang, W.; Gan, S.; Vezzoli, A.; Davidson, R. J.; Milan, D. C.; Luzyanin, K. V.; Higgins, S. J.; Nichols, R. J.; Beeby, A.; Low, P. J. ACS Nano 2016, 10, 5212. doi: 10.1021/acsnano.6b00786 doi: 10.1021/acsnano.6b00786
       

  130. [130]

       Chang, S.; He, J.; Lin, L.; Zhang, P.; Liang, F.; Young, M.; Huang, S.; Lindsay, S. Nanotechnology 2009, 20, 185102. doi: 10.1088/0957-4484/20/18/185102 doi: 10.1088/0957-4484/20/18/185102
       

  131. [131]

       Chang, S.; Huang, S.; He, J.; Liang, F.; Zhang, P.; Li, S.; Chen, X.; Sankey, O.; Lindsay, S. Nano Lett. 2010, 10, 1070. doi: 10.1021/nl1001185 doi: 10.1021/nl1001185
       

  132. [132]

       Chang, S.; He, J.; Kibel, A.; Lee, M.; Sankey, O.; Zhang, P.; Lindsay, S. Nat. Nanotechnol. 2009, 4, 297. doi: 10.1038/nnano.2009.48 doi: 10.1038/nnano.2009.48
       

  133. [133]

       Huang, S.; He, J.; Chang, S.; Zhang, P.; Liang, F.; Li, S.; Tuchband, M.; Fuhrmann, A.; Ros, R.; Lindsay, S. Nat. Nanotechnol. 2010, 5, 868. doi: 10.1038/nnano.2010.213 doi: 10.1038/nnano.2010.213
       

  134. [134]

       Wheeler, D. A.; Srinivasan, M.; Egholm, M.; Shen, Y.; Chen, L.; McGuire, A.; He, W.; Chen, Y. J.; Makhijani, V.; Roth, G. T. Nature 2008, 452, 872. doi: 10.1038/nature06884 doi: 10.1038/nature06884
       

•