Directed Rotations of Single Porphyrin Molecules Controlled by Localized Force SpectroscopyClick to copy article linkArticle link copied!
- Rémy Pawlak
- Sweetlana Fremy
- Shigeki Kawai
- Thilo Glatzel
- Hongjuan Fang
- Leslie-Anne Fendt
- François Diederich
- Ernst Meyer
Abstract

Directed molecular repositioning is a key step toward the build up of molecular machines. To artificially generate and control the motion of molecules on a surface, excitations by light, chemical, or electrical energy have been demonstrated. Here, the application of local mechanical forces is implemented to achieve directed rotations of molecules. Three-dimensional force spectroscopy with sub-Ångström precision is used to characterize porphyrin derivatives with peripheral carbonitrile groups. Extremely small areas on these molecules (≈100 × 100 pm2) are revealed which can be used to control rotations. In response to the local mechanical forces, the molecular structure elastically deforms and then changes its conformation, which leads to its rotation. Depending on the selection of one of four submolecular areas, the molecule is either rotated clockwise or counterclockwise.
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(31)
, 13062-13068. https://doi.org/10.1021/acs.jpcc.1c08935
- Alfred John Weymouth, Elisabeth Riegel, Bianca Simmet, Oliver Gretz, Franz J. Giessibl. Lateral Force Microscopy Reveals the Energy Barrier of a Molecular Switch. ACS Nano 2021, 15
(2)
, 3264-3271. https://doi.org/10.1021/acsnano.0c09965
- Amanda M. Larson, Tedros A. Balema, Percy Zahl, Alex C. Schilling, Dario J. Stacchiola, E. Charles H. Sykes. Hypothetical Efficiency of Electrical to Mechanical Energy Transfer during Individual Stochastic Molecular Switching Events. ACS Nano 2020, 14
(12)
, 16558-16564. https://doi.org/10.1021/acsnano.0c04082
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(6)
, 6947-6954. https://doi.org/10.1021/acsnano.9b01852
- Hong-Liang Lu, Yun Cao, Jing Qi, Anne Bakker, Cristian A. Strassert, Xiao Lin, Karl-Heinz Ernst, Shixuan Du, Harald Fuchs, Hong-Jun Gao. Modification of the Potential Landscape of Molecular Rotors on Au(111) by the Presence of an STM Tip. Nano Letters 2018, 18
(8)
, 4704-4709. https://doi.org/10.1021/acs.nanolett.8b01019
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(10)
, 9930-9940. https://doi.org/10.1021/acsnano.7b03955
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(6)
, 3607-3614. https://doi.org/10.1021/acs.jpcc.6b11873
- Soichiro Yoshimoto, Teppei Kawamoto, Toru Okawara, Yoshio Hisaeda, and Masaaki Abe . Conformational Change in Molecular Assembly of Nickel(II) Tetra(n-propyl)porphycene Triggered by Potential Manipulation. Langmuir 2016, 32
(51)
, 13635-13639. https://doi.org/10.1021/acs.langmuir.6b03782
- Rémy Pawlak, Wengen Ouyang, Alexander E. Filippov, Lena Kalikhman-Razvozov, Shigeki Kawai, Thilo Glatzel, Enrico Gnecco, Alexis Baratoff, Quanshui Zheng, Oded Hod, Michael Urbakh, and Ernst Meyer . Single-Molecule Tribology: Force Microscopy Manipulation of a Porphyrin Derivative on a Copper Surface. ACS Nano 2016, 10
(1)
, 713-722. https://doi.org/10.1021/acsnano.5b05761
- Shiro Yamazaki, Keisuke Maeda, Yoshiaki Sugimoto, Masayuki Abe, Vladimír Zobač, Pablo Pou, Lucia Rodrigo, Pingo Mutombo, Ruben Pérez, Pavel Jelínek, and Seizo Morita . Interplay between Switching Driven by the Tunneling Current and Atomic Force of a Bistable Four-Atom Si Quantum Dot. Nano Letters 2015, 15
(7)
, 4356-4363. https://doi.org/10.1021/acs.nanolett.5b00448
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(1)
, 519-532. https://doi.org/10.1021/cm401999f
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(12)
, 5803-5807. https://doi.org/10.1021/nl402243s
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(8)
, 7370-7376. https://doi.org/10.1021/nn403097p
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(10)
https://doi.org/10.1002/smll.202410652
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(7)
, 5826-5834. https://doi.org/10.1007/s12274-024-6539-z
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(2)
https://doi.org/10.1103/PhysRevX.12.021059
- Yan Li, Qi Zheng, Xiao Chang, Li Huang, Xiao Lin, Zhi-Hai Cheng, Hong-Jun Gao, , , . Atomic, molecular, charge manipulation and application of atomic force microscopy. Acta Physica Sinica 2021, 70
(13)
, 136802. https://doi.org/10.7498/aps.70.20202129
- Parveen Dagar, Jayanta Bera, Appala Naidu Gandi, Lakshya Daukiya, Giriraj Vyas, Satyajit Sahu. Voltage Induced Molecular Motors Constitute the Smallest Self‐Assembled Molecular Electronic Counter. Advanced Materials Interfaces 2020, 7
(18)
https://doi.org/10.1002/admi.202000383
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(35)
, 7808-7822. https://doi.org/10.1002/chem.201905602
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(15)
https://doi.org/10.1103/PhysRevB.100.155427
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(11)
https://doi.org/10.1103/PhysRevLett.121.116101
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(15)
, 3950-3972. https://doi.org/10.1002/ange.201703509
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(15)
, 3888-3908. https://doi.org/10.1002/anie.201703509
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(23)
https://doi.org/10.1063/1.5008503
- Ayhan Yurtsever, Masayuki Abe, Seizo Morita, Yoshiaki Sugimoto. Role of lateral forces on atom manipulation process on Si(111)-
(
7
×
7
)
surface in dynamic force microscopy. Physical Review B 2017, 96
(15)
https://doi.org/10.1103/PhysRevB.96.155412
- R Pawlak, S Kawai, T Meier, T Glatzel, A Baratoff, E Meyer. Single-molecule manipulation experiments to explore friction and adhesion. Journal of Physics D: Applied Physics 2017, 50
(11)
, 113003. https://doi.org/10.1088/1361-6463/aa599d
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- Niko Pavliček, Leo Gross. Generation, manipulation and characterization of molecules by atomic force microscopy. Nature Reviews Chemistry 2017, 1
(1)
https://doi.org/10.1038/s41570-016-0005
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(1)
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- J. Michael Gottfried. Surface chemistry of porphyrins and phthalocyanines. Surface Science Reports 2015, 70
(3)
, 259-379. https://doi.org/10.1016/j.surfrep.2015.04.001
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(1)
https://doi.org/10.1038/srep13143
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(4)
, 475-496. https://doi.org/10.1002/celc.201402399
- Rémy Pawlak, Shigeki Kawai, Thilo Glatzel, Ernst Meyer. Single Molecule Force Spectroscopy. 2015, 195-222. https://doi.org/10.1007/978-3-319-15588-3_11
- Masayuki Abe, Yoshiaki Sugimoto, Seizo Morita. Manipulation and Spectroscopy Using AFM/STM at Room Temperature. 2015, 51-69. https://doi.org/10.1007/978-3-319-15588-3_4
- Thilo Glatzel. Mechanical and Electrical Properties of Single Molecules. 2015, 25-47. https://doi.org/10.1007/978-3-319-17401-3_2
- Mehmet Z. Baykara. Noncontact Atomic Force Microscopy for Atomic-Scale Characterization of Material Surfaces. 2015, 273-316. https://doi.org/10.1007/978-3-662-44551-8_8
- G. Meyer, L. Gross, J. Repp. 3.10 Manipulation of surfaces with the methods of scanning probe microscopy: Data. 2015, 90-99. https://doi.org/10.1007/978-3-662-47736-6_42
- Shigeki Kawai, Matthias Koch, Enrico Gnecco, Ali Sadeghi, Rémy Pawlak, Thilo Glatzel, Jutta Schwarz, Stefan Goedecker, Stefan Hecht, Alexis Baratoff, Leonhard Grill, Ernst Meyer. Quantifying the atomic-level mechanics of single long physisorbed molecular chains. Proceedings of the National Academy of Sciences 2014, 111
(11)
, 3968-3972. https://doi.org/10.1073/pnas.1319938111
- Jorge Echeverria, Serge Monturet, Christian Joachim. One-way rotation of a molecule-rotor driven by a shot noise. Nanoscale 2014, 6
(5)
, 2793. https://doi.org/10.1039/c3nr05814j
- Christian Wagner, Norman Fournier, F Stefan Tautz, Ruslan Temirov. The role of surface corrugation and tip oscillation in single-molecule manipulation with a non-contact atomic force microscope. Beilstein Journal of Nanotechnology 2014, 5 , 202-209. https://doi.org/10.3762/bjnano.5.22
- Seizo Morita. Atomically resolved force microscopy. Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films 2013, 31
(5)
https://doi.org/10.1116/1.4803094
- Khaoula Boukari, Philippe Sonnet, Eric Duverger. DFT‐D Studies of Single Porphyrin Molecule on Doped Boron Silicon Surfaces. ChemPhysChem 2012, 13
(17)
, 3945-3951. https://doi.org/10.1002/cphc.201200578
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