Ab initio calculations; Electron transport measurements; Molecular switches; Oligothiophenes; Photoswitching; Pi-conjugated system; Switching process; Trans-cis isomerization; Electronic, Optical and Magnetic Materials; Energy (all); Physical and Theoretical Chemistry; Surfaces, Coatings and Films; Physics - Mesoscopic Systems and Quantum Hall Effect; General Energy
Abstract :
[en] We report the electron-transport properties of a new photoaddressable molecular switch. The switching process relies on a new concept based on linear π-conjugated dynamic systems, in which the geometry and, hence, the electronic properties of an oligothiophene chain can be reversibly modified by the photochemical trans-cis isomerization of an azobenzene unit fixed in a lateral loop. Electron-transport measurements through self-assembled monolayers on gold, in contact with an eGaIn top contact, showed switching with a conductance ratio of up to 103. Ab initio calculations were used to identify the most energetically stable conformations of the molecular switch; the corresponding calculated conductances qualitatively explain the trend observed in the photoswitching experiments.
Disciplines :
Chemistry
Author, co-author :
Lenfant, S. ; Institute for Electronics Microelectronics and Nanotechnology (IEMN), CNRS, Villeneuve d'Ascq, France
Viero, Y.; Institute for Electronics Microelectronics and Nanotechnology (IEMN), CNRS, Villeneuve d'Ascq, France
Krzeminski, C.; Institute for Electronics Microelectronics and Nanotechnology (IEMN), CNRS, Villeneuve d'Ascq, France
Vuillaume, D. ; Institute for Electronics Microelectronics and Nanotechnology (IEMN), CNRS, Villeneuve d'Ascq, France
Demeter, D.; MOLTECH-Anjou, CNRS, Université d'Angers, Angers, France
Dobra, I.; MOLTECH-Anjou, CNRS, Université d'Angers, Angers, France
Oçafrain, M.; MOLTECH-Anjou, CNRS, Université d'Angers, Angers, France
Blanchard, P.; MOLTECH-Anjou, CNRS, Université d'Angers, Angers, France
Roncali, J. ; MOLTECH-Anjou, CNRS, Université d'Angers, Angers, France
Van Dyck, Colin ; Université de Mons - UMONS > Faculté des Sciences > Service Chimie Physique Théorique
Cornil, Jérôme ; Université de Mons - UMONS > Faculté des Sciences > Service de Chimie des matériaux nouveaux
Language :
English
Title :
New Photomechanical Molecular Switch Based on a Linear π-Conjugated System
Publication date :
08 June 2017
Journal title :
Journal of Physical Chemistry. C, Nanomaterials and interfaces
Agence Nationale de la Recherche Belgian American Educational Foundation Fonds De La Recherche Scientifique - FNRS Seventh Framework Programme
Funding text :
We acknowledge financial support from EU FP7 FET Project SYMONE (Grant 318597) and ANR Project SYNAPTOR (Grant 12BS0301001). C.V.D. was supported by a Gustave Boe.l.Sofina Fellowship of the Belgian American Educational Foundation (BAEF). The work in Mons was supported by the Belgian National Fund for Scientific Research. J.C. is an FNRS research director.
Commentary :
Full manuscript and supporting information, J. Phys. Chem.
C,published on line (2017)
Pace, G.; Ferri, V.; Grave, C.; Elbing, M.; Von Hanisch, C.; Zharnikov, M.; Mayor, M.; Rampi, M. A.; Samori, P. Cooperative Light-Induced Molecular Movements of Highly Ordered Azobenzene Self-Assembled Monolayers Proc. Natl. Acad. Sci. U. S. A. 2007, 104, 9937-9942 10.1073/pnas.0703748104
Ferri, V.; Elbing, M.; Pace, G.; Dickey, M. D.; Zharnikov, M.; Samori, P.; Mayor, M.; Rampi, M. A. Light-Powered Electrical Switch Based on Cargo-Lifting Azobenzene Monolayers Angew. Chem., Int. Ed. 2008, 47, 3407-3409 10.1002/anie.200705339
Kumar, A. S.; Ye, T.; Takami, T.; Yu, B.-C.; Flatt, A. K.; Tour, J. M.; Weiss, P. S. Reversible Photo-Switching of Single Azobenzene Molecules in Controlled Nanoscale Environments Nano Lett. 2008, 8, 1644-1648 10.1021/nl080323+
Mativetsky, J. M.; Pace, G.; Elbing, M.; Rampi, M. A.; Mayor, M.; Samori, P. Azobenzenes as Light-Controlled Molecular Electronic Switches in Nanoscale Metal-Molecule-Metal Junctions J. Am. Chem. Soc. 2008, 130, 9192-9193 10.1021/ja8018093
Smaali, K.; Lenfant, S.; Karpe, S.; Oçafrain, M.; Blanchard, P.; Deresmes, D.; Godey, S.; Rochefort, A.; Roncali, J.; Vuillaume, D. High On-Off Conductance Switching Ratio in Optically-Driven Self-Assembled Conjugated Molecular Systems ACS Nano 2010, 4, 2411-2421 10.1021/nn100295x
Crivillers, N.; Liscio, A.; Di Stasio, F.; Van Dyck, C.; Osella, S.; Cornil, D.; Mian, S.; Lazzerini, G. M.; Fenwick, O.; Orgiu, E.; Reinders, F.; Braun, S.; Fahlman, M.; Mayor, M.; Cornil, J.; Palermo, V.; Cacialli, F.; Samori, P. Photoinduced Work Function Changes by Isomerization of a Densely Packed Azobenzene-Based SAM on Au: A Joint Experimental and Theoretical Study Phys. Chem. Chem. Phys. 2011, 13, 14302-14310 10.1039/c1cp20851a
Osella, S.; Samorì, P.; Cornil, J. Photoswitching Azobenzene Derivatives in Single Molecule Junctions: A Theoretical Insight into the I/ V Characteristics J. Phys. Chem. C 2014, 118, 18721-18729 10.1021/jp504582a
Dulic, D.; van der Molen, S. J.; Kudernac, T.; Jonkman, H. T.; de Jong, J. J. D.; Bowden, T. N.; van Esch, J.; Feringa, B. L.; van Wees, B. J. One-Way Optoelectronic Switching of Photochromic Molecules on Gold Phys. Rev. Lett. 2003, 91, 207402 10.1103/PhysRevLett.91.207402
Katsonis, N.; Kudernac, T.; Walko, M.; Van Der Molen, S. J.; Van Wees, B. J.; Feringa, B. L. Reversible Conductance Switching of Single Diarylethenes on a Gold Surface Adv. Mater. 2006, 18, 1397-1400 10.1002/adma.200600210
Kronemeijer, A. J.; Akkerman, H. B.; Kudernac, T.; Van Wees, B. J.; Feringa, B. L.; Blom, P. W. M.; De Boer, B. Reversible Conductance Switching in Molecular Devices Adv. Mater. 2008, 20, 1467-1473 10.1002/adma.200800053
Kim, Y.; Hellmuth, T. J.; Sysoiev, D.; Pauly, F.; Pietsch, T.; Wolf, J.; Erbe, A.; Huhn, T.; Groth, U.; Steiner, U. E.; Scheer, E. Charge Transport Characteristics of Diarylethene Photoswitching Single-Molecule Junctions Nano Lett. 2012, 12, 3736-3742 10.1021/nl3015523
Van Dyck, C.; Geskin, V.; Kronemeijer, A. J.; De Leeuw, D. M.; Cornil, J. Impact of Derivatization on Electron Transmission Through Dithienylethene-Based Photoswitches in Molecular Junctions Phys. Chem. Chem. Phys. 2013, 15, 4392-4404 10.1039/c3cp44132f
Herder, M.; Schmidt, B. M.; Grubert, L.; Pätzel, M.; Schwarz, J.; Hecht, S. Improving the Fatigue Resistance of Diarylethene Switches J. Am. Chem. Soc. 2015, 137, 2738-2747 10.1021/ja513027s
Katsonis, N.; Lubomska, M.; Pollard, M. M.; Feringa, B.; Rudolf, P. Synthetic Light-Activated Molecular Switches and Motors on Surfaces Prog. Surf. Sci. 2007, 82, 407-434 10.1016/j.progsurf.2007.03.011
Fahrenbach, A. C.; Warren, S. C.; Incorvati, J. T.; Avestro, A.-J.; Barnes, J. C.; Stoddart, J. F.; Grzybowski, B. A. Organic Switches for Surfaces and Devices Adv. Mater. 2013, 25, 331-348 10.1002/adma.201201912
Woitellier, S.; Launay, J.-P.; Joachim, C. The Possibility of Molecular Switching: Theoretical Study of (NH3)5Ru-4,4′-BIPY-Ru(NH3)5)5+ Chem. Phys. 1989, 131, 481-488 10.1016/0301-0104(89)80193-4
Pauly, F.; Viljas, J. K.; Cuevas, J. C.; Schön, G. Density-Functional Study of Tilt-Angle and Temperature-Dependent Conductance in Biphenyl Dithiol Single-Molecule Junctions Phys. Rev. B: Condens. Matter Mater. Phys. 2008, 77, 155312 10.1103/PhysRevB.77.155312
Samanta, P. M.; Tian, W.; Datta, S.; Henderson, J. I.; Kubiak, C. Electronic Conduction Through Organic Molecules Phys. Rev. B: Condens. Matter Mater. Phys. 1996, 53, R7626-R7629 10.1103/PhysRevB.53.R7626
Nishizawa, S.; Hasegawa, J.-y.; Matsuda, K. Theoretical Investigation of the Dependence of Exchange Interaction on Dihedral Angle between Two Aromatic Rings in a Wire Unit Chem. Lett. 2014, 43, 530-532 10.1246/cl.131115
Venkataraman, L.; Klare, J. E.; Nuckolls, C.; Hybertsen, M. S.; Steigerwald, M. L. Dependence of Single-Molecule Junction Conductance on Molecular Conformation Nature 2006, 442, 904-907 10.1038/nature05037
Vonlanthen, D.; Mishchenko, A.; Elbing, M.; Neuburger, M.; Wandlowski, T.; Mayor, M. Chemically Controlled Conductivity: Torsion-Angle Dependence in a Single-Molecule Biphenyldithiol Junction Angew. Chem., Int. Ed. 2009, 48, 8886-8890 10.1002/anie.200903946
Mishchenko, A.; Vonlanthen, D.; Meded, V.; Bürkle, M.; Li, C.; Pobelov, I. V.; Bagrets, A.; Viljas, J. K.; Pauly, F.; Evers, F.; Mayor, M.; Wandlowski, T. Influence of Conformation on Conductance of Biphenyl-Dithiol Single-Molecule Contacts Nano Lett. 2010, 10, 156-163 10.1021/nl903084b
Wang, L.-J.; Yong, A.; Zhou, K.-G.; Tan, L.; Ye, J.; Wu, G.-P.; Xu, Z.-G.; Zhang, H.-L. Conformation-Controlled Electron Transport in Single-Molecule Junctions Containing Oligo(phenylene ethynylene) Derivatives Chem.-Asian J. 2013, 8, 1901-1909 10.1002/asia.201300264
Jousselme, B.; Blanchard, P.; Gallego-Planas, N.; Delaunay, J.; Allain, M.; Richomme, P.; Levillain, E.; Roncali, J. Photomechanical Actuation and Manipulation of the Electronic Properties of Linear π-Conjugated Systems J. Am. Chem. Soc. 2003, 125, 2888-2889 10.1021/ja029754z
Delorme, N.; Bardeau, J. F.; Bulou, A.; Poncin-Epaillard, F. Azobenzene-Containing Monolayer with Photoswitchable Wettability Langmuir 2005, 21, 12278-12282 10.1021/la051517x
Chiechi, R. C.; Weiss, E. A.; Dickey, M. D.; Whitesides, G. M. Eutectic Gallium-Indium (EGaIn): A Moldable Liquid Metal for Electrical Characterization of Self-Assembled Monolayers Angew. Chem., Int. Ed. 2008, 47, 142-144 10.1002/anie.200703642
Cuevas, J. C.; Scheer, E. Molecular Electronics: An Introduction to Theory and Experiment; World Scientific: Singapore, 2010.
Bilić, A.; Reimers, J. R.; Hush, N. S. The Structure, Energetics, and Nature of the Chemical Bonding of Phenylthiol Adsorbed on the Au(111) Surface: Implications for Density-Functional Calculations of Molecular-Electronic Conduction J. Chem. Phys. 2005, 122, 094708 10.1063/1.1850455
Reus, W. F.; Thuo, M. M.; Shapiro, N. D.; Nijhuis, C. A.; Whitesides, G. M. The SAM, Not the Electrodes, Dominates Charge Transport in Metal-Monolayer//Ga2O3/Gallium-Indium Eutectic Junctions ACS Nano 2012, 6, 4806-4822 10.1021/nn205089u
Wan, A.; Jiang, L.; Sangeeth, C. S. S.; Nijhuis, C. A. Reversible Soft Top-Contacts to Yield Molecular Junctions with Precise and Reproducible Electrical Characteristics Adv. Funct. Mater. 2014, 24, 4442-4456 10.1002/adfm.201304237
Magoga, M.; Joachim, C. Conductance of Molecular Wires Connected or Bonded In Parallel Phys. Rev. B: Condens. Matter Mater. Phys. 1999, 59, 16011-16021 10.1103/PhysRevB.59.16011
Reuter, M. G.; Hersam, M. C.; Seideman, T.; Ratner, M. A. Signatures of Cooperative Effects and Transport Mechanisms in Conductance Histograms Nano Lett. 2012, 12, 2243-2248 10.1021/nl204379j
Simeone, F. C.; Yoon, H. J.; Thuo, M. M.; Barber, J. R.; Smith, B.; Whitesides, G. M. Defining the Value of Injection Current and Effective Electrical Contact Area for eGaIn-Based Molecular Tunneling Junctions J. Am. Chem. Soc. 2013, 135, 18131-18144 10.1021/ja408652h
Jiang, L.; Sangeeth, C. S. S.; Wan, A.; Vilan, A.; Nijhuis, C. A. Defect Scaling with Contact Area in eGaIn-Based Junctions: Impact on Quality, Joule Heating, and Apparent Injection Current J. Phys. Chem. C 2015, 119, 960-969 10.1021/jp511002b
Stranick, S. J.; Parikh, A. N.; Tao, Y.-T.; Allara, D. L.; Weiss, P. S. Phase Separation Of Mixed-Composition Self-Assembled Monolayers Into Nanometer Scale Molecular Domains J. Phys. Chem. 1994, 98, 7636-7646 10.1021/j100082a040
Folkers, J. P.; Laibinis, P. E.; Whitesides, G. M.; Deutch, J. Phase Behavior of Two-Component Self-Assembled Monolayers of Alkanethiolates on Gold J. Phys. Chem. 1994, 98, 563-571 10.1021/j100053a035
Jousselme, B.; Blanchard, P.; Levillain, E.; Delaunay, J.; Allain, M.; Richomme, P.; Rondeau, D.; Gallego-Planas, N.; Roncali, J. Crown-Annelated Oligothiophenes as Model Compounds for Molecular Actuation J. Am. Chem. Soc. 2003, 125, 1363-1370 10.1021/ja026819p
Yu, C. J.; Chong, Y.; Kayyem, J. F.; Gozin, M. Soluble Ferrocene Conjugates for Incorporation into Self-Assembled Monolayers J. Org. Chem. 1999, 64, 2070-2079 10.1021/jo982392m
Jousselme, B.; Blanchard, P.; Gallego-Planas, N.; Delaunay, J.; Allain, M.; Richomme, P.; Levillain, E.; Roncali, J. Photomechanical Control of the Electronic Properties of Linear π-Conjugated Systems Chem.-Eur. J. 2003, 9, 5297-5306 10.1002/chem.200305010
