SFB 658:
Elementary Processes in Molecular Switches at Surfaces
Subject Area
Physics
Chemistry
Term
from 2005 to 2017
Project identifier
Deutsche Forschungsgemeinschaft (DFG) - Project number 12489635
Final Report Year
2017
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
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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
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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
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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
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Spatial periodicity in molecular switching, Nat. Nanotechnol. 3, 649 (2008)
C. Dri, M. V. Peters, J. Schwarz, S. Hecht, L. Grill
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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
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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
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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
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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
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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
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Competition of Superconducting Phenomena and Kondo Screening at the Nanoscale, Science 332, 940 (2011)
K. J. Franke, G. Schulze, J. I. Pascual
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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
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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
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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
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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
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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
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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
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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
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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
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Energy Transfer in Nanotube-Perylene Complexes, Adv. Funct. Mater. 22, 3921 (2012)
F. Ernst, T. Heek, A. Setaro, R. Haag, S. Reich
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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Tuning the Magnetic Anisotropy of Single Molecules, Nano Letters 15, 4024 (2015)
B. W. Heinrich, L. Braun, J. I. Pascual, K. J. Franke
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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
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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
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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
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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
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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
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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
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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
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Proposal for dark exciton based chemical sensors, Nat. Commun. 8, 14776 (2017)
M. Feierabend, G. Berghäuser, A. Knorr, E. Malic
DFG Programme
Collaborative Research Centres
Completed projects
-
A01 - Fundamental switching mechanisms of molecules on metal surfaces investigated with scanning tunneling microscopy
(Project Head
Franke, Katharina
)
-
A02 - Conformational changes of single molecules on semiconductor surfaces induced by inelastic electron tunneling processes
(Project Head
Fölsch, Stefan
)
-
A03 - Electron transport through single molecules and graphene
(Project Head
Rabe, Jürgen P.
)
-
A04 - Excitation and structural transformation of single adsorbed molecules induced by localized optical fields
(Project Head
Elsässer, Thomas
)
-
A05 - Complex switching units and molecular architectures, studied by scanning tunneling microscopy
(Project Heads
Grill, Leonhard
;
Wolf, Martin
)
-
A06 - Molecular switches on carbon surfaces
(Project Heads
Reich, Stephanie
;
Setaro, Ph.D., Antonio
)
-
B01 - Molecular switching processes at surfaces: Optical-induced charge transfer and molecular orientation
(Project Head
Tegeder, Petra
)
-
B02 - Charge transfer dynamics and switching efficiency in photochromic molecular ensembles at surfaces
(Project Heads
Gahl, Cornelius
;
Weinelt, Martin
)
-
B03 - Magnetism and lateral ordering phenomena of switchable molecules at surfaces
(Project Head
Kuch, Wolfgang
)
-
B04 - Optische und magnetooptische Untersuchung von molekularen Magneten und photoinduzierten Dipolen auf Oberflächen
(Project Heads
Fumagalli, Paul
;
Rüdt, Christoph Benedikt
)
-
B05 - Surface-adsorbed switchable ensembles of metal complexes
(Project Head
Grohmann, Andreas
)
-
B06 - Photoswitchable units for fundamental processes on surfaces
(Project Head
Rück-Braun, Karola
)
-
B07 - Functional imin- and diazo-switching units
(Project Head
Haag, Rainer
)
-
B08 - Switching architectures for controlling charge transport
(Project Head
Hecht, Stefan
)
-
B09 - Molecular switching in self-assembled monolayers at liquid-solid interfaces
(Project Heads
Campen, Ph.D., Richard Kramer
;
Wolf, Martin
)
-
B10 - Structure, excitonic coupling and cooperative dynamics of switches on surfaces: Real-time and in situ x-ray structure investigations
(Project Head
Kowarik, Stefan M.
)
-
C01 - Ab initio Theorie des Ladungstransports durch einzelne Moleküle
(Project Heads
Gross, Eberhard K. U.
;
Kurth, Stefan
)
-
C02 - Quantum theory for light- and electron-driven molecular switches at surfaces: structure and dynamics
(Project Heads
Klamroth, Tillmann
;
Saalfrank, Peter
)
-
C03 - Ab initio Untersuchungen zur Funktionalität molekularer Schalter auf Oberflächen
(Project Heads
Reuter, Karsten
;
Scheffler, Matthias
)
-
C04 - Conformational changes and magnetic switching in deposited molecular structures
(Project Heads
Brouwer, Piet W.
;
von Oppen, Felix
)
-
C05 - Theory of excitation transfer in functionalized carbon nanotubes
(Project Heads
Knorr, Andreas
;
Malic, Ermin
)
-
C06 - Excitations of molecular switches on surfaces: Insight from first-principles
(Project Head
Draxl, Claudia
)
-
MGK - Integrated Research Training Group
(Project Heads
Kuch, Wolfgang
;
Reich, Stephanie
)
-
V - Zentrale Aufgaben
(Project Heads
von Oppen, Felix
;
Weinelt, Martin
)
-
Z - Photoelectron spectroscopy for the chemical analysis of molecular switches at surfaces
(Project Heads
Kuch, Wolfgang
;
Rück-Braun, Karola
;
Weinelt, Martin
)