A reversible single-molecule switch based on activated antiaromaticity

Yin, Xiaodong; Zang, Yaping; Zhu, Liangliang; Low, Jonathan Z.; Liu, Zhen-Fei; Cui, Jing; Neaton, Jeffrey B.; Venkataraman, Latha; Campos, Luis M.

doi:10.1126/sciadv.aao2615

Title: A reversible single-molecule switch based on activated antiaromaticity

Journal Article · Fri Oct 27 00:00:00 EDT 2017 · Science Advances

DOI:https://doi.org/10.1126/sciadv.aao2615· OSTI ID:1432216

^[1];

^[2]; Zhu, Liangliang ^[3];

^[1];

^[4];

^[2];

^[4];

^[5];

^[1]

Columbia Univ., New York, NY (United States). Dept. of Chemistry
Columbia Univ., New York, NY (United States). Dept. of Applied Physics
Fudan Univ., Shanghai (China)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
Columbia Univ., New York, NY (United States). Dept. of Chemistry; Columbia Univ., New York, NY (United States). Dept. of Applied Physics

Single-molecule electronic devices provide researchers with an unprecedented ability to relate novel physical phenomena to molecular chemical structures. Typically, conjugated aromatic molecular backbones are relied upon to create electronic devices, where the aromaticity of the building blocks is used to enhance conductivity. We capitalize on the classical physical organic chemistry concept of Hückel antiaromaticity by demonstrating a single-molecule switch that exhibits low conductance in the neutral state and, upon electrochemical oxidation, reversibly switches to an antiaromatic high-conducting structure. We form single-molecule devices using the scanning tunneling microscope–based break-junction technique and observe an on/off ratio of ~70 for a thiophenylidene derivative that switches to an antiaromatic state with 6-4-6-p electrons. Through supporting nuclear magnetic resonance measurements, we show that the doubly oxidized core has antiaromatic character and we use density functional theory calculations to rationalize the origin of the high-conductance state for the oxidized single-molecule junction. Together, our work demonstrates how the concept of antiaromaticity can be exploited to create single-molecule devices that are highly conducting.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1432216

Journal Information:: Science Advances, Vol. 3, Issue 10; ISSN 2375-2548

Publisher:: AAASCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 80 works

Citation information provided by
Web of Science

References (47)

Thermoelectricity in Molecular Junctions Reddy, P.; Jang, S.-Y.; Segalman, R. A. Science, Vol. 315, Issue 5818, p. 1568-1571 https://doi.org/10.1126/science.1137149	journal	March 2007
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Electron Transport in Molecular Wire Junctions Nitzan, A. Science, Vol. 300, Issue 5624 https://doi.org/10.1126/science.1081572	journal	May 2003
Measurement of Single-Molecule Resistance by Repeated Formation of Molecular Junctions Xu, B. Science, Vol. 301, Issue 5637 https://doi.org/10.1126/science.1087481	journal	August 2003
Tunable Charge Transport in Single-Molecule Junctions via Electrolytic Gating Capozzi, Brian; Chen, Qishui; Darancet, Pierre Nano Letters, Vol. 14, Issue 3 https://doi.org/10.1021/nl404459q	journal	February 2014
Mechanically controlled binary conductance switching of a single-molecule junction Quek, Su Ying; Kamenetska, Maria; Steigerwald, Michael L. Nature Nanotechnology, Vol. 4, Issue 4 https://doi.org/10.1038/nnano.2009.10	journal	March 2009
Twisted but Conjugated: Building Blocks for Low Bandgap Polymers Chiu, Chien-Yang; Wang, Hengbin; Brunetti, Fulvio G. Angewandte Chemie International Edition, Vol. 53, Issue 15 https://doi.org/10.1002/anie.201400674	journal	March 2014
Enhancing thermoelectric properties of single-walled carbon nanotubes using halide compounds at room temperature and above. Kumanek, Bogumiła; Stando, Grzegorz; Stando, Paweł Apollo - University of Cambridge Repository https://doi.org/10.17863/cam.68746	text	January 2021
Single-molecule diodes with high rectification ratios through environmental control Capozzi, Brian; Xia, Jianlong; Adak, Olgun Nature Nanotechnology, Vol. 10, Issue 6 https://doi.org/10.1038/nnano.2015.97	journal	May 2015
Dependence of single-molecule junction conductance on molecular conformation Venkataraman, Latha; Klare, Jennifer E.; Nuckolls, Colin Nature, Vol. 442, Issue 7105 https://doi.org/10.1038/nature05037	journal	August 2006
Antiaromaticity Breslow, Ronald Accounts of Chemical Research, Vol. 6, Issue 12 https://doi.org/10.1021/ar50072a001	journal	December 1973
Molecular rectifiers Aviram, Arieh; Ratner, Mark A. Chemical Physics Letters, Vol. 29, Issue 2 https://doi.org/10.1016/0009-2614(74)85031-1	journal	November 1974
Current-Induced Hydrogen Tautomerization and Conductance Switching of Naphthalocyanine Molecules Liljeroth, Peter; Repp, Jascha; Meyer, Gerhard Science, Vol. 317, Issue 5842, p. 1203-1206 https://doi.org/10.1126/science.1144366	journal	August 2007
Amine−Gold Linked Single-Molecule Circuits: Experiment and Theory Quek, Su Ying; Venkataraman, Latha; Choi, Hyoung Joon Nano Letters, Vol. 7, Issue 11 https://doi.org/10.1021/nl072058i	journal	November 2007
Density-functional method for nonequilibrium electron transport Brandbyge, Mads; Mozos, José-Luis; Ordejón, Pablo Physical Review B, Vol. 65, Issue 16, Article No. 165401 https://doi.org/10.1103/PhysRevB.65.165401	journal	March 2002
Frustrated Rotations in Single-Molecule Junctions Park, Young S.; Widawsky, Jonathan R.; Kamenetska, Maria Journal of the American Chemical Society, Vol. 131, Issue 31 https://doi.org/10.1021/ja903731m	journal	August 2009
Electron transport in molecular junctions Tao, N. J. Nature Nanotechnology, Vol. 1, Issue 3 https://doi.org/10.1038/nnano.2006.130	journal	December 2006
Coulomb blockade and the Kondo effect in single-atom transistors Park, Jiwoong; Pasupathy, Abhay N.; Goldsmith, Jonas I. Nature, Vol. 417, Issue 6890 https://doi.org/10.1038/nature00791	journal	June 2002
Kondo resonance in a single-molecule transistor Liang, Wenjie; Shores, Matthew P.; Bockrath, Marc Nature, Vol. 417, Issue 6890 https://doi.org/10.1038/nature00790	journal	June 2002
Nucleus-Independent Chemical Shifts (NICS) as an Aromaticity Criterion Chen, Zhongfang; Wannere, Chaitanya S.; Corminboeuf, Clémence Chemical Reviews, Vol. 105, Issue 10 https://doi.org/10.1021/cr030088+	journal	September 2005
Renormalization of Molecular Electronic Levels at Metal-Molecule Interfaces Neaton, J. B.; Hybertsen, Mark S.; Louie, Steven G. Physical Review Letters, Vol. 97, Issue 21 https://doi.org/10.1103/PhysRevLett.97.216405	journal	November 2006
Chemical principles of single-molecule electronics Su, Timothy A.; Neupane, Madhav; Steigerwald, Michael L. Nature Reviews Materials, Vol. 1, Issue 3 https://doi.org/10.1038/natrevmats.2016.2	journal	February 2016
Electrochemical Single-Molecule Transistors with Optimized Gate Coupling Osorio, Henrry M.; Catarelli, Samantha; Cea, Pilar Journal of the American Chemical Society, Vol. 137, Issue 45 https://doi.org/10.1021/jacs.5b08431	journal	November 2015
Twisted but Conjugated: Building Blocks for Low Bandgap Polymers Chiu, Chien-Yang; Wang, Hengbin; Brunetti, Fulvio G. Angewandte Chemie, Vol. 126, Issue 15 https://doi.org/10.1002/ange.201400674	journal	March 2014
Quasiparticle Spectra from a Nonempirical Optimally Tuned Range-Separated Hybrid Density Functional Refaely-Abramson, Sivan; Sharifzadeh, Sahar; Govind, Niranjan Physical Review Letters, Vol. 109, Issue 22 https://doi.org/10.1103/PhysRevLett.109.226405	journal	November 2012
Covalently bonded single-molecule junctions with stable and reversible photoswitched conductivity Jia, C.; Migliore, A.; Xin, N. Science, Vol. 352, Issue 6292 https://doi.org/10.1126/science.aaf6298	journal	June 2016
A Molecular Switch Based on Potential-Induced Changes of Oxidation State Chen, Fan; He, Jin; Nuckolls, Colin Nano Letters, Vol. 5, Issue 3 https://doi.org/10.1021/nl0478474	journal	March 2005
The Electrical Properties of Biphenylenes Schneebeli, Severin; Kamenetska, Maria; Foss, Frank Organic Letters, Vol. 12, Issue 18 https://doi.org/10.1021/ol1017036	journal	September 2010
Aromatic and antiaromatic ring currents in a molecular nanoring Peeks, Martin D.; Claridge, Timothy D. W.; Anderson, Harry L. Nature, Vol. 541, Issue 7636 https://doi.org/10.1038/nature20798	journal	December 2016
Summation of Nucleus Independent Chemical Shifts as a Measure of Aromaticity Mills, Nancy S.; Llagostera, Kathleen B. The Journal of Organic Chemistry, Vol. 72, Issue 24 https://doi.org/10.1021/jo7013609	journal	November 2007
The SIESTA method for ab initio order- N materials simulation Soler, José M.; Artacho, Emilio; Gale, Julian D. Journal of Physics: Condensed Matter, Vol. 14, Issue 11 https://doi.org/10.1088/0953-8984/14/11/302	journal	March 2002
Strain and HÃ¼ckel Aromaticity: Driving Forces for a Promising New Generation of Electron Acceptors in Organic Electronics Brunetti, F. âG.; Gong, X.; Tong, M. Angewandte Chemie, Vol. 122, Issue 3 https://doi.org/10.1002/ange.200905117	journal	January 2010
Nucleus-Independent Chemical Shifts (NICS) as an Aromaticity Criterion Chen, Zhongfang; Wannere, Chaitanya S.; Corminboeuf, Clemence ChemInform, Vol. 37, Issue 4 https://doi.org/10.1002/chin.200604277	journal	January 2006
CHEMISTRY: Enhanced: Whence Molecular Electronics? Flood, A. H. Science, Vol. 306, Issue 5704 https://doi.org/10.1126/science.1106195	journal	December 2004
Preparation and characterization of STM tips for electrochemical studies Nagahara, L. A.; Thundat, T.; Lindsay, S. M. Review of Scientific Instruments, Vol. 60, Issue 10 https://doi.org/10.1063/1.1140590	journal	October 1989
Biphenylene Lothrop, Warren C. Journal of the American Chemical Society, Vol. 63, Issue 5 https://doi.org/10.1021/ja01850a007	journal	May 1941
Aromaticity Decreases Single-Molecule Junction Conductance. Chen, Wenbo; Li, Haixing; Widawsky, Jonathan R. Journal of the American Chemical Society, Vol. 136, Issue 3 https://doi.org/10.1021/ja411143s	journal	January 2014
Strain and Hückel Aromaticity: Driving Forces for a Promising New Generation of Electron Acceptors in Organic Electronics Brunetti, F. G.; Gong, X.; Tong, M. Angewandte Chemie International Edition, Vol. 49, Issue 3 https://doi.org/10.1002/anie.200905117	journal	December 2009
Dications of Tetrabenzofulvalenes. Paratropicity and .sigma. Donation in Perpendicular Antiaromatic Systems Malandra, James L.; Mills, Nancy S.; Kadlecek, Daniel E. Journal of the American Chemical Society, Vol. 116, Issue 25 https://doi.org/10.1021/ja00104a074	journal	December 1994
Reliable Energy Level Alignment at Physisorbed Molecule–Metal Interfaces from Density Functional Theory Egger, David A.; Liu, Zhen-Fei; Neaton, Jeffrey B. Nano Letters, Vol. 15, Issue 4 https://doi.org/10.1021/nl504863r	journal	March 2015
Mapping the Transmission Functions of Single-Molecule Junctions Capozzi, Brian; Low, Jonathan Z.; Xia, Jianlong Nano Letters, Vol. 16, Issue 6 https://doi.org/10.1021/acs.nanolett.6b01592	journal	May 2016
Formation and Evolution of Single-Molecule Junctions Kamenetska, M.; Koentopp, M.; Whalley, A. C. Physical Review Letters, Vol. 102, Issue 12 https://doi.org/10.1103/PhysRevLett.102.126803	journal	March 2009
Formation and Evolution of Single Molecule Junctions Kamenetska, M.; Koentopp, M.; Whalley, A. C. arXiv https://doi.org/10.48550/arxiv.0901.1134	text	January 2009
Quasiparticle spectra from a non-empirical optimally-tuned range-separated hybrid density functional Refaely-Abramson, Sivan; Sharifzadeh, Sahar; Govind, Niranjan arXiv https://doi.org/10.48550/arxiv.1203.2357	text	January 2012
Density functional method for nonequilibrium electron transport Brandbyge, Mads; Mozos, Jose-Luis; Ordejon, Pablo arXiv https://doi.org/10.48550/arxiv.cond-mat/0110650	text	January 2001
Dependence of Single Molecule Junction Conductance on Molecular Conformation Venkataraman, Latha; Klare, Jennifer E.; Nuckolls, Colin arXiv https://doi.org/10.48550/arxiv.cond-mat/0607836	text	January 2006
One-Way Optoelectronic Switching of Photochromic Molecules on Gold Dulić, Diana; van der Molen, S. J.; Kudernac, T. Physical Review Letters, Vol. 91, Issue 20 https://doi.org/10.1103/physrevlett.91.207402	journal	November 2003

Cited By (21)

Quantum interference mediated vertical molecular tunneling transistors Jia, Chuancheng; Famili, Marjan; Carlotti, Marco Science Advances, Vol. 4, Issue 10 https://doi.org/10.1126/sciadv.aat8237	journal	October 2018
A sub 20 nm metal-conjugated molecule junction acting as a nitrogen dioxide sensor Wani, Ishtiaq H.; Jafri, S. Hassan M.; Warna, John Nanoscale, Vol. 11, Issue 14 https://doi.org/10.1039/c8nr08417c	journal	January 2019
Non-aromatic annulene-based aggregation-induced emission system via aromaticity reversal process Zhao, Zheng; Zheng, Xiaoyan; Du, Lili Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-10818-5	journal	July 2019
Dinaphthobenzo[1,2:4,5]dicyclobutadiene: Antiaromatic and Orthogonally Tunable Electronics and Packing Jin, Zexin; Yao, Ze-Fan; Barker, Kayla P. Angewandte Chemie, Vol. 131, Issue 7 https://doi.org/10.1002/ange.201812581	journal	January 2019
Side-group chemical gating via reversible optical and electric control in a single molecule transistor Meng, Linan; Xin, Na; Hu, Chen Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09120-1	journal	March 2019
Electron transport behavior of quinoidal heteroacene-based junctions: effective electron-transport pathways and quantum interference. Cheng, Na; Chen, Feng; Durkan, Colm Apollo - University of Cambridge Repository https://doi.org/10.17863/cam.33809	text	January 2018
Isomeric effects tuning the electron transport in carotenoid derivatives: from ohmic to rectifier behavior Guedes, A. M.; Corrêa, S. M.; Ferreira, D. F. S. Journal of Molecular Modeling, Vol. 24, Issue 9 https://doi.org/10.1007/s00894-018-3767-8	journal	August 2018
Two-electron transfer stabilized by excited-state aromatization Kim, Jinseok; Oh, Juwon; Park, Seongchul Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-12986-w	journal	November 2019
Direct Au–C contacts based on biphenylene for single molecule circuits Arasu, Narendra P.; Vázquez, Héctor Physical Chemistry Chemical Physics, Vol. 20, Issue 15 https://doi.org/10.1039/c8cp00613j	journal	January 2018
A theoretical study on a series of polycyclic conjugated hydrocarbons—dinaphthobenzo[1,2:4,5]dicyclobutadienes with tunable charge transport properties by controlling [ N ]phenylenes and (anti)aromaticity Yin, Hang; Zheng, Daoyuan; Qiao, Yan Journal of Materials Chemistry C, Vol. 7, Issue 22 https://doi.org/10.1039/c9tc01660k	journal	January 2019
Multicenter-Bond-Based Quantum Interference in Charge Transport Through Single-Molecule Carborane Junctions Tang, Chun; Chen, Lijue; Zhang, Longyi Angewandte Chemie International Edition, Vol. 58, Issue 31 https://doi.org/10.1002/anie.201904521	journal	June 2019
Versatile electrochemical approaches towards the fabrication of molecular electronic devices Sachan, Pradeep; Mondal, Prakash Chandra The Analyst, Vol. 145, Issue 5 https://doi.org/10.1039/c9an01948k	journal	January 2020
Exploring antiaromaticity in single-molecule junctions formed from biphenylene derivatives Gantenbein, Markus; Li, Xiaohui; Sangtarash, Sara Nanoscale, Vol. 11, Issue 43 https://doi.org/10.1039/c9nr05375a	journal	January 2019
Dinaphthobenzo[1,2:4,5]dicyclobutadiene: Antiaromatic and Orthogonally Tunable Electronics and Packing Jin, Zexin; Yao, Ze-Fan; Barker, Kayla P. Angewandte Chemie International Edition, Vol. 58, Issue 7 https://doi.org/10.1002/anie.201812581	journal	January 2019
Transition from stochastic events to deterministic ensemble average in electron transfer reactions revealed by single-molecule conductance measurement Li, Yueqi; Wang, Hui; Wang, Zixiao Proceedings of the National Academy of Sciences, Vol. 116, Issue 9 https://doi.org/10.1073/pnas.1814825116	journal	February 2019
Electrical and spin switches in single‐molecule junctions Ke, Guojun; Duan, Chunhui; Huang, Fei InfoMat, Vol. 2, Issue 1 https://doi.org/10.1002/inf2.12068	journal	December 2019
Multicenter‐Bond‐Based Quantum Interference in Charge Transport Through Single‐Molecule Carborane Junctions Tang, Chun; Chen, Lijue; Zhang, Longyi Angewandte Chemie, Vol. 131, Issue 31 https://doi.org/10.1002/ange.201904521	journal	June 2019
Electronegativity, symmetry, and bond strength intrinsically control charge transport through five-membered single-molecule junction Mijbil, Zainelabideen Y. The European Physical Journal B, Vol. 92, Issue 10 https://doi.org/10.1140/epjb/e2019-100361-7	journal	October 2019
Electron transport behavior of quinoidal heteroacene-based junctions: effective electron-transport pathways and quantum interference Cheng, Na; Chen, Feng; Durkan, Colm Physical Chemistry Chemical Physics, Vol. 20, Issue 45 https://doi.org/10.1039/c8cp05901b	journal	January 2018
Spin Logic Gates Operated by Protonation and Magnetism in Molecular Combinational Circuits Zhao, Wenkai; Zou, Dongqing; Sun, Zhaopeng Advanced Theory and Simulations https://doi.org/10.1002/adts.201900057	journal	April 2019
Concepts in the design and engineering of single-molecule electronic devices Xin, Na; Guan, Jianxin; Zhou, Chenguang Nature Reviews Physics, Vol. 1, Issue 3 https://doi.org/10.1038/s42254-019-0022-x	journal	February 2019