Citation: Huang Zhichao, Dai Yazhong, Wen Xiaojie, Liu Dan, Lin Yuxuan, Xu Zhen, Pei Jian, Wu Kai. Conformational Switching of Verdazyl Radicals on Au(111)[J]. Acta Physico-Chimica Sinica, ;2020, 36(1): 190704. doi: 10.3866/PKU.WHXB201907043 shu

Conformational Switching of Verdazyl Radicals on Au(111)

Beijing National Laboratory for Molecular Sciences (BNLMS), College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China

Corresponding author: Pei Jian, jianpei@pku.edu.cn Wu Kai, kaiwu@pku.edu.cn
Received Date: 15 July 2019
Revised Date: 19 August 2019
Accepted Date: 22 August 2019
Available Online: 30 January 2019
Fund Project: The project was supported by the National Natural Science Foundation of China (21821004) and the Ministry of Science and Technology of China (2017YFA0204702)the Ministry of Science and Technology of China 2017YFA0204702the National Natural Science Foundation of China 21821004

Pure organic radical molecules on metal surfaces are of great significance in exploration of the electron spin behavior. However, only a few of them are investigated in surface studies due to their poor thermal stability. The adsorption and conformational switching of two verdazyl radical molecules, namely, 1, 5-biisopropyl-3-(benzo[b]benzo[4,5]thieno[2, 3-d]thiophen-2-yl)-6-oxoverdazyl (B2P) and 1, 5-biisopropyl-3-(benzo[b]benzo[4,5]thieno[2, 3-d]thiophen-4-yl)-6-oxoverdazyl (B4P), are studied by scanning tunneling microscopy (STM) and density functional theory (DFT). The adsorbed B2P molecules on Au(111) form dimers, trimers and tetramers without any ordered assembly structure in which two distinct appearances of B2P in STM images are observed and assigned to be its "P" and "T" conformations. The "P" conformation molecules appear in the STM image with a large elliptical protrusion and two small ones of equal size, while the "T" ones appear with a large protrusion and two small ones of different size. Likewise, the B4P molecules on Au(111) form dimers at low coverage, strip structure at medium coverage and assembled structure at high coverage which also consists of above-mentioned two conformations. Both B2P molecules and B4P molecules are held together by weak intermolecular interaction rather than chemical bond. STM tip induced conformational switching of both verdayzl radicals is observed at the bias voltage of +2.0 V. The "T" conformation of B2P can be switched to the "P" while the "P" conformation of B4P can be switched to the "T" one. For both molecules, such a conformational switching is irreversible. The DFT calculations with Perdew-Burke-Ernzerhof version exchange-correlation functional are used to optimize the model structure and simulate the STM images. STM images of several possible molecular conformations with different isopropyl orientation and different tilt angle between verdazyl radical and Au(111) surface are simulated. For conformations with different isopropyl orientation, the STM simulated images are similar, while different tilt angles of verdazyl radical lead to significantly different STM simulated images. Combined STM experiments and DFT simulations reveal that the conformational switching originates from the change of tilting angle between the verdazyl radical and Au(111) surface. The tilt angles in "P" and "T" conformations are 0° and 50°, respectively. In this study, two different adsorption conformations of verdazyl radicals on the Au(111) surface are presented and their exact adsorption structures are identified. This study provides a possible way to study the relationship between the electron spin and configuration conversion of pure organic radical molecules and a reference for designing more conformational switchable radical molecules that can be employed as interesting molecular switches.
- Verdazyl radical,
- Scanning tunneling microscopy,
- Density functional theory,
- Electron spin
1. [1]
  Ternes, M.; Heinrich, A. J.; Schneider, W. D. J. Phys. Condens. Matter. 2009, 21, 053001. doi: 10.1088/0953-8984/21/5/053001 doi: 10.1088/0953-8984/21/5/053001
2. [2]
  Huang, Z. C.; Zhang, Y. J.; He, Y.; Song, H. J.; Yin, C.; Wu, K. Chem. Soc. Rev. 2017, 46, 1955. doi: 10.1039/c6cs00891g doi: 10.1039/c6cs00891g
3. [3]
  Cornia, A.; Fabretti, A. C.; Pacchioni, M.; Zobbi, L.; Bonacchi, D.; Caneschi, A.; Gatteschi, D.; Biagi, R.; Del Pennino, U.; De Renzi, V.; et al. Angew. Chem. Int. Ed. 2003, 42, 1645. doi: 10.1002/anie.200350981 doi: 10.1002/anie.200350981
4. [4]
  Sun, K.; Park, K.; Xie, J.; Luo, J.; Yuan, H.; Xiong, Z.; Wang, J.; Xue, Q. ACS Nano 2013, 7, 6825. doi: 10.1021/nn401827h doi: 10.1021/nn401827h
5. [5]
  Zhao, A. D.; Li, Q. X.; Chen, L.; Xiang, H. J.; Wang, W. H.; Pan, S.; Wang, B.; Xiao, X. D.; Yang, J. L.; Hou, J. G.; et al. Science 2005, 309, 1542. doi: 10.1126/science.1113449 doi: 10.1126/science.1113449
6. [6]
  Liu, L. W.; Yang, K.; Jiang, Y. H.; Song, B. Q.; Xiao, W. D.; Li, L. F.; Zhou, H. T.; Wang, Y. L.; Du, S. X.; Ouyang, M.; et al. Sci. Rep. 2013, 3, 1210. doi: 10.1038/srep01210 doi: 10.1038/srep01210
7. [7]
  Chen, X.; Fu, Y. S.; Ji, S. H.; Zhang, T.; Cheng, P.; Ma, X. C.; Zou, X. L.; Duan, W. H.; Jia, J. F.; Xue, Q. K. Phys. Rev. Lett. 2008, 101, 197208. doi: 10.1103/PhysRevLett.101.197208 doi: 10.1103/PhysRevLett.101.197208
8. [8]
  Zhang, Y. J.; Wang, Y. F.; Liao, P. L.; Wang, K.; Huang, Z. C.; Liu, J.; Chen, Q. W.; Jiang, J. Z.; Wu, K. ACS Nano 2018, 12, 2991. doi: 10.1021/acsnano.8b00751 doi: 10.1021/acsnano.8b00751
9. [9]
  Bernien, M.; Miguel, J.; Weis, C.; Ali, M. E.; Kurde, J.; Krumme, B.; Panchmatia, P. M.; Sanyal, B.; Piantek, M.; Srivastava, P.; et al. Phys. Rev. Lett. 2009, 102, 047202. doi: 10.1103/PhysRevLett.102.047202 doi: 10.1103/PhysRevLett.102.047202
10. [10]
  Zhang, Y. H.; Kahle, S.; Herden, T.; Stroh, C.; Mayor, M.; Schlickum, U.; Ternes, M.; Wahl, P.; Kern, K. Nat. Commun. 2013, 4, 1. doi: 10.1038/ncomms3110 doi: 10.1038/ncomms3110
11. [11]
  Liu, J.; Isshiki, H.; Katoh, K.; Morita, T.; Breedlove, B. K.; Yamashita, M.; Komeda, T. J. Am. Chem. Soc. 2012, 135, 651. doi: 10.1021/ja303510g doi: 10.1021/ja303510g
12. [12]
  Casu, M. B. Acc. Chem. Res. 2018, 51, 753. doi: 10.1021/acs.accounts.7b00612 doi: 10.1021/acs.accounts.7b00612
13. [13]
  Gallagher, N.; Zhang, H.; Junghoefer, T.; Giangrisostomi, E.; Ovsyannikov, R.; Pink, M.; Rajca, S.; Casu, M. B.; Rajca, A. J. Am. Chem. Soc. 2019, 141, 4764. doi: 10.1021/jacs.9b00558 doi: 10.1021/jacs.9b00558
14. [14]
  Karan, S.; Li, N.; Zhang, Y.; He, Y.; Hong, I. P.; Song, H.; Lu, J. T.; Wang, Y.; Peng, L.; Wu, K.; et al. Phys. Rev. Lett. 2016, 116, 027201. doi: 10.1103/PhysRevLett.116.027201 doi: 10.1103/PhysRevLett.116.027201
15. [15]
  Ciastek, S.; Jasiński, M.; Kaszyński, P. RSC Adv. 2015, 5, 33328. doi: 10.1039/c5ra04119h doi: 10.1039/c5ra04119h
16. [16]
  Segall, M. D.; Lindan, P. J. D.; Probert, M. J.; Pickard, C. J.; Hasnip, P. J.; Clark, S. J.; Payne, M. C. J. Phys. Condens. Matter 2002, 14, 2717. doi: 10.1088/0953-8984/14/11/301 doi: 10.1088/0953-8984/14/11/301
17. [17]
  Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996, 77, 3865. doi: 10.1103/PhysRevLett.77.3865 doi: 10.1103/PhysRevLett.77.3865
1. [1]
  Yutong Xiong , Ting Meng , Wendi Luo , Bin Tu , Shuai Wang , Qingdao Zeng . Molecular conformational effects on co-assembly systems of low-symmetric carboxylic acids investigated by scanning tunneling microscopy. Chinese Journal of Structural Chemistry, 2025, 44(2): 100511-100511. doi: 10.1016/j.cjsc.2025.100511
2. [2]
  Yuxiang Zhang , Jia Zhao , Sen Lin . Nitrogen doping retrofits the coordination environment of copper single-atom catalysts for deep CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(11): 100415-100415. doi: 10.1016/j.cjsc.2024.100415
3. [3]
  Wei Chen , Pieter Cnudde . A minireview to ketene chemistry in zeolite catalysis. Chinese Journal of Structural Chemistry, 2024, 43(11): 100412-100412. doi: 10.1016/j.cjsc.2024.100412
4. [4]
  Yi Liu , Peng Lei , Yang Feng , Shiwei Fu , Xiaoqing Liu , Siqi Zhang , Bin Tu , Chen Chen , Yifan Li , Lei Wang , Qing-Dao Zeng . Topologically engineering of π-conjugated macrocycles: Tunable emission and photochemical reaction toward multi-cyclic polymers. Chinese Chemical Letters, 2024, 35(10): 109571-. doi: 10.1016/j.cclet.2024.109571
5. [5]
  Junjie Duan , Dan Chen , Long Chen , Shuying Li , Ting Chen , Dong Wang . 2D hexagonal tessellations sustained by Br···Br/H contacts: From regular to semiregular to k-uniform tilings. Chinese Chemical Letters, 2025, 36(3): 110445-. doi: 10.1016/j.cclet.2024.110445
6. [6]
  Lingling Su , Qunyan Wu , Congzhi Wang , Jianhui Lan , Weiqun Shi . Theoretical design of polyazole based ligands for the separation of Am(Ⅲ)/Eu(Ⅲ). Chinese Chemical Letters, 2024, 35(8): 109402-. doi: 10.1016/j.cclet.2023.109402
7. [7]
  Yu-Hang Li , Shuai Gao , Lu Zhang , Hanchun Chen , Chong-Chen Wang , Haodong Ji . Insights on selective Pb adsorption via O 2p orbit in UiO-66 containing rich-zirconium vacancies. Chinese Chemical Letters, 2024, 35(8): 109894-. doi: 10.1016/j.cclet.2024.109894
8. [8]
  Xin-Tong Zhao , Jin-Zhi Guo , Wen-Liang Li , Jing-Ping Zhang , Xing-Long Wu . Two-dimensional conjugated coordination polymer monolayer as anode material for lithium-ion batteries: A DFT study. Chinese Chemical Letters, 2024, 35(6): 108715-. doi: 10.1016/j.cclet.2023.108715
9. [9]
  Jiajun Wang , Guolin Yi , Shengling Guo , Jianing Wang , Shujuan Li , Ke Xu , Weiyi Wang , Shulai Lei . Computational design of bimetallic TM₂@g-C₉N₄ electrocatalysts for enhanced CO reduction toward C₂ products. Chinese Chemical Letters, 2024, 35(7): 109050-. doi: 10.1016/j.cclet.2023.109050
10. [10]
  Fanjun Kong , Yixin Ge , Shi Tao , Zhengqiu Yuan , Chen Lu , Zhida Han , Lianghao Yu , Bin Qian . Engineering and understanding SnS_0.5Se_0.5@N/S/Se triple-doped carbon nanofibers for enhanced sodium-ion batteries. Chinese Chemical Letters, 2024, 35(4): 108552-. doi: 10.1016/j.cclet.2023.108552
11. [11]
  Weiping Xiao , Yuhang Chen , Qin Zhao , Danil Bukhvalov , Caiqin Wang , Xiaofei Yang . Constructing the synergistic active sites of nickel bicarbonate supported Pt hierarchical nanostructure for efficient hydrogen evolution reaction. Chinese Chemical Letters, 2024, 35(12): 110176-. doi: 10.1016/j.cclet.2024.110176
12. [12]
  Ze Zhang , Lei Yang , Jin-Ru Liu , Hao Hu , Jian-Li Mi , Chao Su , Bei-Bei Xiao , Zhi-Min Ao . Improved oxygen electrocatalysis at FeN₄ and CoN₄ sites via construction of axial coordination. Chinese Chemical Letters, 2025, 36(2): 110013-. doi: 10.1016/j.cclet.2024.110013
13. [13]
  Chaozheng He , Menghui Xi , Chenxu Zhao , Ran Wang , Ling Fu , Jinrong Huo . Highly N₂ dissociation catalyst: Ir(100) and Ir(110) surfaces. Chinese Chemical Letters, 2025, 36(3): 109671-. doi: 10.1016/j.cclet.2024.109671
14. [14]
  Mianfeng Li , Haozhi Wang , Zijun Yang , Zexiang Yin , Yuan Liu , Yingmei Bian , Yang Wang , Xuerong Zheng , Yida Deng . Synergistic enhancement of alkaline hydrogen evolution reaction by role of Ni-Fe LDH introducing frustrated Lewis pairs via vacancy-engineered. Chinese Chemical Letters, 2025, 36(3): 110199-. doi: 10.1016/j.cclet.2024.110199
15. [15]
  Teng Wang , Jiachun Cao , Juan Li , Didi Li , Zhimin Ao . A novel photocatalytic mechanism of volatile organic compounds degradation on BaTiO₃ under visible light: Photo-electrons transfer from photocatalyst to pollutant. Chinese Chemical Letters, 2025, 36(3): 110078-. doi: 10.1016/j.cclet.2024.110078
16. [16]
  Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1409-1422. doi: 10.11862/CJIC.20240007
17. [17]
  Xian-Fa Jiang , Chongyun Shao , Zhongwen Ouyang , Zhao-Bo Hu , Zhenxing Wang , You Song . Generating electron spin qubit in metal-organic frameworks via spontaneous hydrolysis. Chinese Chemical Letters, 2024, 35(7): 109011-. doi: 10.1016/j.cclet.2023.109011
18. [18]
  Xiaochen Zhang , Fei Yu , Jie Ma . 多角度数理模拟在电容去离子中的前沿应用. Acta Physico-Chimica Sinica, 2024, 40(11): 2311026-. doi: 10.3866/PKU.WHXB202311026
19. [19]
  Zhengzhong Zhu , Shaojun Hu , Zhi Liu , Lipeng Zhou , Chongbin Tian , Qingfu Sun . A cationic radical lanthanide organic tetrahedron with remarkable coordination enhanced radical stability. Chinese Chemical Letters, 2025, 36(2): 109641-. doi: 10.1016/j.cclet.2024.109641
20. [20]
  Yinglian LI , Chengcheng ZHANG , Xinyu ZHANG , Xinyi WANG . Spin crossover in [Co(pytpy)₂]²⁺ complexes modified by organosulfonate anions. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1162-1172. doi: 10.11862/CJIC.20240087

Get Citation

PDF

XML

Metrics

PDF Downloads(11)
Abstract views(246)
HTML views(30)

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