SFB 658: Elementary Processes in Molecular Switches at Surfaces
Chemistry
Final Report Abstract
Molecular switches came to the attention of the wider public at the latest with the award of the Nobel Prize for Chemistry 2016 to Jean-Pierre Sauvage, Fraser Stoddart und Ben Feringa – for inventing and synthesizing artificial molecular machines. External stimuli change the conformation or the configuration of molecular switches which can therefore realize complex functions on the shortest length scales and with a high degree of reproducibility. Nature exploits molecular switching in human vision which relies on the isomerization of retinal between microscopically distinct cis- and trans-states. The Collaborative Research Center Sfb 658 ”Elementary processes in molecular switches at surfaces“ aimed at anchoring molecular switches at surfaces and developing new methods to control the functionalities of these anchored molecules. A major challenge was that the molecules’ switching properties were strongly affected or even completely suppressed by the surface. This led us to develop strategies for optimizing the coupling between switch and surface. Specifically, we synthesized new molecular switches with various spacers which allowed us to tailor the interaction between switch and surface both in planar and in vertical adsorption geometries. As a result of an intense cooperation between chemical synthesis and surface physics, we could ultimately realize a large variety of switching processes on surfaces. This includes transcis-isomerization, tautomerization, ring-opening/ring-closing reactions and switching in magnetic molecules on metal and semiconductor surfaces as well as on graphene and carbon nanotube substrates. After overcoming substantial initial difficulties, switching molecules at surfaces became routine. Through intensive collaboration between experiment and theory, this allowed us to unravel and optimize the elementary processes of switching events in considerable detail both in individual molecules and molecular ensembles. Specific configurations of molecular switches could be realized and stabilized through atomic scale manipulation, and contacted both in vertical and lateral configurations, for instance for realizing a single-molecule transistor. Self-organization was exploited to realize molecular layers whose optical and electric properties could be effectively switched through light with minimal aging. Switching could be enhanced in networks through cooperativity. The spin state of magnetic molecules could be stabilized and switched through the coupling to the substrate. Moreover, switching processes were exploited to manipulate the physical and chemical properties of carbon nanotubes such as solubility, biocompatibility, light emission, or carrier density. A crucial condition for the success of Sfb 658 was the intense collaboration across disciplines which persisted through all funding periods. Of the total of about 430 publications in peer-reviewed journals, more thab 25% resulted from a cooperation of two or more subprojects. Over the course of the project, seven project leaders received and followed outside offers, reflecting the impact and the quality of our research. We are proud that within Sfb 658, 85 students completed their dissertations in this cutting edge research field. Last but not least, Sfb 658 will have a lasting impact on the Focus Area Nanoscale at Freie Universität Berlin and the wider Berlin research landscape through its role in four new professorial appointments.
Publications
- Electric Field-Induced Isomerization of Azobenzene by STM, J. Am. Chem. Soc. 128, 14446 (2006)
M. Alemani, M. V. Peters, S. Hecht, K.-H. Rieder, F. Moresco, L. Grill
(See online at https://doi.org/10.1021/ja065449s) - Substrate-induced magnetic ordering and switching of iron porphyrin molecules, Nat. Mater. 6, 516 (2007)
H. Wende, M. Bernien, J. Luo, C. Sorg, N. Ponpandian, J. Kurde, J. Miguel, M. Piantek, X. Xu, Ph. Eckhold, W. Kuch, K. Baberschke, P. M. Panchmatia, B. Sanyal, P. M. Oppeneer, O. Eriksson
(See online at https://doi.org/10.1038/nmat1932) - Excitation mechanism in the photoisomerization of a surface-bound azobenzene derivative: Role of the metallic substrate, J. Chem. Phys. 129, 164102 (2008)
S. Hagen, P. Kate, F. Leyssner, D. Nandi, M. Wolf, P. Tegeder
(See online at https://doi.org/10.1063/1.2997343) - Spatial periodicity in molecular switching, Nat. Nanotechnol. 3, 649 (2008)
C. Dri, M. V. Peters, J. Schwarz, S. Hecht, L. Grill
(See online at https://doi.org/10.1038/nnano.2008.269) - Franck-Condon blockade in suspended carbon nanotube quantum dots, Nature Phys. 5, 327 (2009)
R. Leturcq, C. Stampfer, K. Inderbitzin, L. Durrer, C. Hierold, E. Mariani, M.G. Schultz, F. von Oppen, and K. Ensslin
(See online at https://doi.org/10.1038/nphys1234) - Reversing the thermal stability of a molecular switch on a gold surface: ring-opening reaction of nitro-spiropyran, J. Am. Chem. Soc. 131, 12729 (2009)
M. Piantek, G. Schulze, M. Koch, K. J. Franke, F. Leyssner, A. Krüger, C. Navío, J. Miguel, M. Bernien, M. Wolf, W. Kuch, P. Tegeder, J. I. Pascual
(See online at https://doi.org/10.1021/ja901238p) - Tailoring the nature of magnetic coupling of Fe-porphyrin molecules to ferromagnetic substrates, Phys. Rev. Lett. 102, 047202 (2009)
M. Bernien, J. Miguel, C. Weis, Md. E. Ali, J. Kurde, B. Krumme, P. M. Panchmatia, B. Sanyal, M. Piantek, P. Srivastava, K. Baberschke, P. M. Oppeneer, O. Eriksson, W. Kuch, H. Wende
(See online at https://doi.org/10.1103/physrevlett.102.047202) - DE 10 2008 053 691.1 (filed 29.10.2008), US 2011/0266326 A1 (filed 29.10.2009), PCT/DE2009/001513 (filed 29.10.2009), WO/2010/048940 (published 6.5.2010), Schneidvorrichtung zum Schneiden von Graphen sowie Verfahren zum Schneiden von Graphen mittels Schneidvorrichtung
N. Severin, S. Kirstein, J.P. Rabe
- Structure and excitonic coupling in self-assembled monolayers of azobenzene-functionalized alkanethiols, J. Am. Chem. Soc. 132, 1831 (2010)
C. Gahl, R. Schmidt, D. Brete, E. McNellis, W. Freyer, R. Carley, K. Reuter, M. Weinelt
(See online at https://doi.org/10.1021/ja903636q) - Competition of Superconducting Phenomena and Kondo Screening at the Nanoscale, Science 332, 940 (2011)
K. J. Franke, G. Schulze, J. I. Pascual
(See online at https://doi.org/10.1126/science.1202204) - DE 10 2009 056 052.1 DPMA filed 26.11.2009, PCT/DE2010/050084 (filed 22.11.2010), WO/2011/063802 (published 03.06.2011), Anordnung mit einem Träger und einer Schicht
N. Severin, M. Dorn, J.P. Rabe
- Imine derivatives on Au(111): Evidence for “inverted” thermal isomerization, ACS Nano 5 2090 (2011)
J. Mielke, F. Leyssner, M. Koch, S. Meyer, Y. Luo, S. Selvanathan, R. Haag, P. Tegeder, L. Grill
(See online at https://doi.org/10.1021/nn103297e) - Light-Orchestrated Macromolecular “Accordions”, Reversible Photoinduced Shrinking of Rigid-Rod Polymers, Angew. Chem. Int. Ed. 50, 12559 (2011)
D. Bléger, T. Liebig, R. Thiermann, M. Maskos, J. P. Rabe, S. Hecht
(See online at https://doi.org/10.1002/anie.201106879) - Microscopic Model of the Optical Absorption of Carbon Nanotubes Functionalized with Molecular Spiropyran Photoswitches, Phys. Rev. Lett. 106, 097401 (2011)
E. Malic, C. Weber, M. Richter, V. Atalla, T. Klamroth, P. Saalfrank, S. Reich, A. Knorr
(See online at https://doi.org/10.1103/physrevlett.106.097401) - US Application 13/044,459, (filed 09.03.2011), PCT/EP 2012/053562 (filed 01.03.2012), WO/2012/119924 (published 13.09.2012), Method of analyzing a substance
A. Kalachev, N. Severin, J.P. Rabe
- Controlled reversible debundling of single-walled carbon nanotubes by photo-switchable dendritic surfactants, Nanoscale 4, 3029 (2012)
C. Kördel, A. Setaro, P. Bluemmel, C.S. Popeney, S. Reich, R. Haag
(See online at https://doi.org/10.1039/c2nr30305a) - Controlled Switching within an Organic Molecule Deliberately Pinned to a Semiconductor Surface, ACS Nano 6, 4190 (2012)
C. Nacci, S. C. Erwin, K. Kanisawa, S. Fölsch
(See online at https://doi.org/10.1021/nn300690n) - Driving a macroscopic oscillator with the stochastic motion of a hydrogen molecule, Science 338, 779 (2012)
C. Lotze, M. Corso, K. J. Franke, F. von Oppen, J.I. Pascual
(See online at https://doi.org/10.1126/science.1227621) - Energy Transfer in Nanotube-Perylene Complexes, Adv. Funct. Mater. 22, 3921 (2012)
F. Ernst, T. Heek, A. Setaro, R. Haag, S. Reich
(See online at https://doi.org/10.1002/adfm.201200784) - Ferromagnetic coupling of mononuclear Fe centers in a self-assembled metal organic network on Au(111), Phys. Rev. Lett. 109, 267207 (2012)
T. R. Umbach, M. Bernien, C. F. Hermanns, A. Krüger, V. Sessi, I. Fernández-Torrente, P. Stoll, J. I. Pascual, K. J. Franke, W. Kuch
(See online at https://doi.org/10.1103/physrevlett.109.267207) - Gating the charge state of a single molecule by local fields, Phys. Rev. Lett. 108, 036801 (2012)
I. Fernandez-Torrente, D. Kreikemeyer-Lorenzo, A. Strozecka, K. J. Franke, J. I. Pascual
(See online at https://doi.org/10.1103/physrevlett.108.036801) - Induction of a photostationary ring-opening-ring-closing state of spiropyran monolayers on the semimetallic Bi(110) surface, Phys. Rev. Lett. 109, 026102 (2012)
G. Schulze, K. J. Franke, J. I. Pascual
(See online at https://doi.org/10.1103/physrevlett.109.026102) - Non-Covalent Functionalization of Individual Nanotubes with Spiropyran-Based Molecular Switches, Adv. Funct. Mater. 22, 2425 (2012)
A. Setaro, P. Bluemmel, C. Maity, S. Hecht, S. Reich
(See online at https://doi.org/10.1002/adfm.201102451) - o-Fluoroazobenzenes as Readily Synthesized Photoswitches Offering Nearly Quantitative Two-Way Isomerization with Visible Light, J. Am. Chem. Soc. 134, 20597 (2012)
D. Bléger, J. Schwarz, A. M. Brouwer, S. Hecht
(See online at https://doi.org/10.1021/ja310323y) - Optically switchable transistor via energy-level phototuning in a bicomponent organic semiconductor, Nat. Chem. 4, 675 (2012)
Orgiu, N. Crivillers, M. Herder, L. Grubert, M, Pätzel, J. Frisch, E. Pavlica, D. T. Duong, G. Bratina, A. Salleo, N. Koch, S. Hecht, P. Samorì
(See online at https://doi.org/10.1038/nchem.1384) - Reversible Change of the Spin State in a Manganese Phthalocyanine by Coordination of CO Molecule, Phys. Rev. Lett. 109, 147202 (2012)
A. Stróżecka, M. Soriano, J. I. Pascual, J. J. Palacios
(See online at https://doi.org/10.1103/physrevlett.109.147202) - Coverage- and Temperature-Controlled Isomerization of an Imine Derivative on Au(111), J. Am. Chem. Soc. 135 4273 (2013)
C. Gahl, D. Brete, F. Leyssner, M. Koch, E. R. McNellis, J. Mielke, R. Carley, L. Grill, K. Reuter, P. Tegeder, M. Weinelt
(See online at https://doi.org/10.1021/ja309330e) - Protection of excited spin states by a superconducting energy gap, Nature Physics 9, 765 (2013)
B. W. Heinrich, L. Braun, J. I. Pascual, K. J. Franke
(See online at https://doi.org/10.1038/nphys2794) - Quantitative IR readout of fulgimide monolayer switching on Si(111) surfaces, Adv. Mater. 25, 416 (2013)
C. H. de Villeneuve, F. Michalik, J. N. Chazalviel, K. Rück-Braun, P. Allongue
(See online at https://doi.org/10.1002/adma.201201546) - Bulk spin-crossover in the complex [FeL(NCS)2] of a tris(pyridyl)ethane-derived N4-ligand-a temperature-dependent crystallographic study, Dalton Transactions 43, 2406 (2014)
D. Wiedemann and A. Grohmann
(See online at https://doi.org/10.1039/c3dt53070a) - Controlling intramolecular hydrogen transfer in a porphycene molecule with single atoms or molecules located nearby, Nat. Chem. 6, 41 (2014)
T. Kumagai, F. Hanke, S. Gawinkowski, J. Sharp, K. Kotsis, J. Waluk, M. Persson, L. Grill
(See online at https://doi.org/10.1038/nchem.1804) - Light-Induced Contraction and Extension of Single Macromolecules on a Modified Graphite Surface, ACS Nano 12, 11987 (2014)
C. L. Lee, T. Liebig, S. Hecht, D. Bléger, J. P. Rabe
(See online at https://doi.org/10.1021/nn505325w) - Gating a single-molecule transistor with individual atoms, Nat. Phys. 11, 640 (2015)
J. Martínez-Blanco, C. Nacci, S. C. Erwin, K. Kanisawa, E. Locane, M. Thomas, F. v. Oppen, P. W. Brouwer, S. Fölsch
(See online at https://doi.org/10.1038/nphys3385) - Highly efficient thermal and light-induced spinstate switching of an Fe(II) complex in direct contact with a solid surface, ACS Nano 9, 8960 (2015)
M. Bernien, H. Naggert, L. M. Arruda, L. Kipgen, F. Nickel, J. Miguel, C. F. Hermanns, A. Krüger, D. Krüger, E. Schierle, E. Weschke, F. Tuczek, W. Kuch
(See online at https://doi.org/10.1021/acsnano.5b02840) - Surface-Induced Selection During in Situ Photoswitching at the Liquid-Solid Interface, Angew. Chem. Int. Ed. 54, 4865 (2015)
S. Bonacchi, M. El Garah, A. Ciesielski, M. Herder, S. Conti, M. Cecchini, S. Hecht and P. Samorì
(See online at https://doi.org/10.1002/anie.201412215) - Tuning the Magnetic Anisotropy of Single Molecules, Nano Letters 15, 4024 (2015)
B. W. Heinrich, L. Braun, J. I. Pascual, K. J. Franke
(See online at https://doi.org/10.1021/acs.nanolett.5b00987) - Cooperative Switching in Nanofibers of Azobenzene Oligomers, Scientific Reports 6, 25605 (2016)
C. Weber, T. Liebig, M.Gensler, A, Zykov, L, Pithan, J. P. Rabe, S. Hecht, D. Bléger, S. Kowarik
(See online at https://doi.org/10.1038/srep25605) - Flexible non-volatile optical memory thin-film transistor device with over 256 distinct levels based on an organic bicomponent blend, Nat. Nanotech. 11, 769 (2016)
T. Leydecker, M. Herder, E. Pavlica, G. Bratina, S. Hecht, E. Orgiu and P. Samorì
(See online at https://doi.org/10.1038/nnano.2016.87) - Sensitized Two-NIR- Photon Z → E Isomerization of a Visible-Light-Addressable Bistable Azobenzene Derivative, Angew. Chem. Int. Ed. 55, 1544 (2016)
J. Moreno, M. Gerecke, L. Grubert, S. Kovalenko, S. Hecht
(See online at https://doi.org/10.1002/anie.201509111) - Visualizing the Role of Molecular Orbitals in Charge Transport through Individual Diarylethene Isomers, ACS Nano 10, 10555 (2016)
G. Reecht, C. Lotze, D. Sysoiev, T. Huhn, K. J. Franke
(See online at https://doi.org/10.1021/acsnano.6b06559) - Electrocatalytic Z→E Isomerization of Azobenzenes, J. Am. Chem. Soc. 139, 335 (2017)
A. Goulet-Hanssens, M. Utecht, D. Mutruc, E. Titov, J. Schwarz, L. Grubert, D. Bléger, P. Saalfrank, S. Hecht
(See online at https://doi.org/10.1021/jacs.6b10822) - Patent No. 16194861.7-1554, A method and a sensor for detecting the presence of molecules with a dipole moment
M. Feierabend, G. Berghäuser, A. Knorr and E. Malic
- Preserving π-conjugation in covalently functionalized carbon nanotubes for optoelectronic applications, Nat. Commun. 8, 14281 (2017)
A. Setaro, M. Adeli, M. Glaeske, D. Przyrembel, T. Bisswanger, G. Gordeev, F. Maschietto, A. Faghani, B. Paulus, M. Weinelt, R. Arenal, R. Haag, S. Reich
(See online at https://doi.org/10.1038/ncomms14281) - Proposal for dark exciton based chemical sensors, Nat. Commun. 8, 14776 (2017)
M. Feierabend, G. Berghäuser, A. Knorr, E. Malic
(See online at https://doi.org/10.1038/ncomms14776)
