SFB 677: Function by Switching
Biology
Computer Science, Systems and Electrical Engineering
Materials Science and Engineering
Medicine
Physics
Final Report Abstract
Switching is the elementary step in most engineering functions and machines. Switches provide the basis of technical and biological processes such as directed transport, pumping, energy conversion, sensing, information storage and processing. Miniaturization of the switching units in electronic circuits and mechanical components triggered an unprecedented development referred to as the second technological revolution that changed our life and society in many aspects. It has been predicted that the so-called third industrial revolution will be based on technologies that can shrink three-dimensional objects. The ultimate limit of miniaturization for the construction of functional objects are molecular switches. Beyond providing superior efficiency, molecular switches and machines are compatible in size and function with biological systems and molecular electronics, and thus allow unprecedented applications and hybrid technologies. The enormous potential of this field has been widely recognized and finally awarded with the Nobel Prize in Chemistry 2016 to Jean-Pierre Sauvage, Fraser Stoddart and Ben Feringa. Summing up, when we started our SFB in 2007 we chose the right topic at the right time. By entering the field at an early stage, we were able to contribute substantially to the development at an internationally competitive level. During three funding periods, our SFB attained worldwide visibility and recognition. A molecular switch is not yet a machine and switching does not necessarily lead to a useful function. To convert a switching event into a function, the molecular switch has to be embedded into a well-defined environment and must interact in a controlled fashion. Consequently, we divided our SFB into three project areas: A: Design, synthesis and characterization in solution, B: immobilization and investigation on surfaces and C: Implementation of switches in materials. In average more than 100 scientists (PhD students, postdocs, professors) from chemistry, physics, materials science and pharmacy collaborated throughout the funding duration. To foster interdisciplinary collaboration, PIs from different fields jointly supervised the majority of projects. Major breakthroughs were achieved in all three areas. New switches with unsurpassed efficiencies (quantum yields, conversion rates and fatigue resistance) and unprecedented functions such as the first magnetically bistable molecules were developed. Two seminal publications were cited each well above 200 times and triggered new research areas and applications, such as the development of light-activatable drugs and functional contrast agents in magnetic resonance imaging. Within project area B, we developed a novel strategy to immobilize molecules on surfaces, the so-called platform concept. Since our publication in 2009, numerous groups worldwide are using our method. Applying our strategy, we discovered a new type of catalysis via a non-adiabatic mechanism mediated by bulk metal surfaces, which might be used to develop new catalysts. Further highlights were the discovery and detailed investigation of spincrossover compounds on surfaces and studies into the electrical conductance of molecular switches and other controlled contacts. Key for the success of SFB677 was the close collaboration of scientists from different disciplines. Among the 400 publications in peer-reviewed journals and 6 patents 21% were joined papers from PIs of different projects and more than 50% include the names of two PIs in the author list. The visibility and quality of our research is documented by the 14 members of the SFB 677 who received outside calls and accepted permanent positions as professors. 75 Dissertations have been completed. Beyond the scientific success, our SFB exerted a major impact on the research priorities of Kiel University. A new research focus, the Kiel Nano Surface and Interface Science (KiNSIS) was kicked off in 2013. We are also particularly proud that SFB members launched two successful startup companies.
Publications
- Orientationally Ordered (7 * 7) Superstructure of C60 on Au(111). Phys. Rev. Lett. 2007, 99, 226105/1-226105/4
G. Schull, R. Berndt
(See online at https://doi.org/10.1103/physrevlett.99.226105) - Conductance of Oriented C60 Molecules. Nano Lett. 2008, 8, 1291-1295
N. Neel, J. Kröger, L. Limot, R. Berndt
(See online at https://doi.org/10.1021/nl073074i) - Highly Efficient Reversible Z−E Photoisomerization of a Bridged Azobenzene with Visible Light through Resolved S1(nπ*) Absorption Bands. J. Am. Chem. Soc. 2009, 131, 15594 - 15595
R. Siewertsen, H. Neumann, B. Buchheim-Stehn, R. Herges, C. Naether, F. Renth, F. Temps
(See online at https://doi.org/10.1021/ja906547d) - Local density of states from constant-current tunneling spectra. Phys. Rev. B: Condens. Matter Mater. Phys. 2009, 80, 125402
M. Ziegler, N. Néel, A. Sperl, J. Kröger, R. Berndt
(See online at https://doi.org/10.1103/PhysRevB.80.125402) - Mounting Freestanding Molecular Functions onto Surfaces: The Platform Approach. J. Am. Chem. Soc. 2009, 131, 442-443
B. Baisch, D. Raffa, U. Jung, O. Magnussen, C. Nicolas, J. Lacour, J. Kubitschke, R. Herges
(See online at https://doi.org/10.1021/ja807923f) - Passing Current through Touching Molecules. Phys. Rev. Lett. 2009, 103, 206803
G. Schull, T. Frederiksen, M. Brandbyge, R. Berndt
(See online at https://doi.org/10.1103/physrevlett.103.206803) - Pushing and Pulling a Sn Ion through an Adsorbed Phthalocyanine Molecule. J. Am. Chem. Soc. 2009, 131, 3639-3643
Y. Wang, J. Kröger, R. Berndt, W. Hofer, Werner
(See online at https://doi.org/10.1021/ja807876c) - Structural and Electronic Properties of Ultrathin Tin-Phthalocyanine Films on Ag(111) at the Single-Molecule Level. Angew. Chem. 2009, 121, 1287-1291
Y. Wang, J. Kröger, R. Berndt, W. Hofer
(See online at https://doi.org/10.1002/ange.200803305) - Supramolecular Patterns controlled by Electron Interference and Direct Intermolecular Interactions. J. Am. Chem. Soc. 2009, 131, 10400-10402
Y. Wang, X. Ge, C. Manzano, J. Kröger, R. Berndt, W. Hofer, H. Tang, J. Cerda
(See online at https://doi.org/10.1021/ja903506s) - Atomic-Scale Control of Electron Transport through Single Molecules. Phys. Rev. Lett. 2010, 104, 176802
Y. Wang, J. Kröger, R. Berndt, H. Vázquez, M. Brandbyge, M. Paulsson
(See online at https://doi.org/10.1103/physrevlett.104.176802) - Coordination-Induced Spin Crossover (CISCO) through Axial Bonding of Substituted Pyridines to Nickel-Porphyrins: sigma-Donor vs pi-Acceptor Effects. Chem. Eur. J. 2010, 16, 9928-9937
S. Thies, C. Bornholdt, F. Köhler, F.D. Sönnichsen, C. Näther, F. Tuczek, R. Herges
(See online at https://doi.org/10.1002/chem.201000603) - CoPc adsorption on Cu(111): Origin of the C4 to C2 symmetry reduction. J. Chem. Phys. 2010, 133, 154701
R. Cuadrado, J.I. Cerdá, Y. Wang, G. Xin, R. Berndt, H. Tang
(See online at https://doi.org/10.1063/1.3502682) - Photoswitching Behavior of Azobenzene-Containing Alkanethiol Self-Assembled Monolayers on Au Surfaces. Langmuir 2010, 26, 13913-13923
U. Jung, O. Filinova, S. Kuhn, D. Zargarani, C. Bornholdt, R. Herges, O. Magnussen
(See online at https://doi.org/10.1021/la1015109) - Spatiotemporal control of nano-optical excitations. Proc. Nat. Acad. Sci. 2010, 107, 5329-5333
M. Aeschlimann, M. Bauer, D. Bayer, T. Brixner, S. Cunovic, F. Dimler, A. Fischer, W. Pfeiffer, M. Rohmer, C. Schneider, F. Steeb, C. Strüber, D.V. Voronine
(See online at https://doi.org/10.1073/pnas.0913556107) - Atomic-scale engineering of electrodes for single-molecule contacts. Nature Nanotech. 2011, 6, 23-27
G. Schull, T. Frederiksen, A. Arnau, D. Sánchez-Portal, R. Berndt
(See online at https://doi.org/10.1038/nnano.2010.215) - Azobenzene-Containing Triazatriangulenium Adlayers on Au(111): Structural and Spectros copic Characterization. Langmuir 2011, 27, 5899-5908
U. Jung, S. Kuhn, U. Cornelissen, F. Tuczek, T. Strunskus, V. Zaporojtchenko, J. Kubitschke, R. Herges, O. Magnussen
(See online at https://doi.org/10.1021/la104654p) - Charge Injection through Single and Double Carbon Bonds. Nano Lett. 2011, 11, 3142-3146
G. Schull, Y.J. Dappe, C. Gonzalez, H. Bulou, R. Berndt
(See online at https://doi.org/10.1021/nl201185y) - Controlled Metalation of a Single Adsorbed Phthalocyanine. Angew. Chem. 2011, 123, 5406-5409
A. Sperl, J. Kröger, R. Berndt
(See online at https://doi.org/10.1002/ange.201100950) - Coverage-Driven Electronic Decoupling of Fe-Phthalocyanine from a Ag(111) Substrate. J. Phys. Chem. C 2011, 115, 12173-12179
T.G. Gopakumar, T. Brumme, J. Kröger, C. Toher, G. Cuniberti, R. Berndt
(See online at https://doi.org/10.1021/jp2038619) - Design of a Perfect Black Absorber at Visible Frequencies Using Plasmonic Metamaterials. Adv. Mater. 2011, 23, 5410-5414
M.K. Hedayati, M. Javaherirahim, B. Mozooni, R. Abdelaziz, A. Tavassolizadeh, V.S.K. Chakravadhanula, V. Zaporojtchenko, T. Strunkus, F. Faupel, M. Elbahri
(See online at https://doi.org/10.1002/adma.201102646) - First observation of light-induced spin change in vacuum deposited thin films of iron spin crossover complexes. J. Chem. Soc. Dalton Trans. 2011, 40, 636
H. Naggert, A. Bannwarth, S. Chemnitz, H. van Hofe, E. Quandt, F. Tuczek
(See online at https://doi.org/10.1039/c1dt10651a) - Magnetic Bistability of Molecules in Homogeneous Solution at Room Temperature. Science 2011, 331, 445-448
S. Venkataramani, U. Jana, M. Dommaschk, F.D. Sönnichsen, F. Tuczek, R. Herges
(See online at https://doi.org/10.1126/science.1201180) - Superior Z→E and E→Z photoswitching dynamics of dihydrodibenzodiazocine, a bridged azobenzene, by S1(nπ*) excitation at λ = 387 and 490 nm. Phys. Chem. Chem. Phys. 2011, 13, 1054-1063
R. Siewertsen, J.B. Schönborn, B. Hartke, F. Renth, F. Temps
(See online at https://doi.org/10.1039/c0cp01148g) - The First Porous MOF with Photoswitchable Linker Molecules. J. Chem. Soc. Dalton Trans. 2011, 40, 4217-4222
A. Modrow, D. Zargarani, R. Herges, N. Stock
(See online at https://doi.org/10.1039/c0dt01629b) - Electron-Induced Spin Crossover of Single Molecules in a Bilayer on Gold. Angew. Chem. Int. Ed. 2012, 51, 6262-6266
T.G. Gopakumar, F. Matino, H. Naggert, A. Bannwarth, F. Tuczek, R. Berndt
(See online at https://doi.org/10.1002/anie.201201203) - FeIII Spin-Crossover Complexes with Photoisomerizable Ligands: Experimental and Theoretical Studies on the Ligand-Driven Light-Induced Spin Change Effect. Eur. J. Inorg. Chem. 2012, 2776-2783
A. Bannwarth, O. Schmidt, G. Peters, F.D. Sönnichsen, W. Thimm, R. Herges, F. Tuczek
(See online at https://doi.org/10.1002/ejic.201101227) - Introducing a photo-switchable azo-functionality inside Cr-MIL-101-NH2 by covalent postsynthetic modification. Dalton Trans. 2012, 41, 8690-8696
A. Modrow, D. Zargarani, R. Herges, N. Stock
(See online at https://doi.org/10.1039/c2dt30672g) - Joining the Un-Joinable: Adhesion Between Low Surface Energy Polymers Using Tetrapodal ZnO Linkers. Adv. Mater. 2012, 24, 5676-5680
X. Jin, J. Strueben, L. Heepe, A. Kovalev, Y.K. Mishra, R. Adelung, S.N. Gorb, A. Staubitz
(See online at https://doi.org/10.1002/adma.201201780) - Light Emission Probing Quantum Shot Noise and Charge Fluctuations at a Biased Molecular Junction. Phys. Rev. Lett. 2012, 109, 186601
N.L. Schneider, J.T. Lu, M. Brandbyge, R. Berndt
(See online at https://doi.org/10.1103/physrevlett.109.186601) - Saccharide-Modified Nanodiamond Conjugates for the Efficient Detection and Removal of Pathogenic Bacteria. Chem. Eur. J. 2012, 18, 6485-6492
M. Hartmann, P. Betz, Y. Sun, S.N. Gorb, T.K. Lindhorst, A. Krueger
(See online at https://doi.org/10.1002/chem.201104069) - A Novel Concept for Self-Reporting Materials: Stress Sensitive Photoluminescence in ZnO Tetrapod Filled Elastomers. Adv. Mater. 2013, 25, 1342-1347
X. Jin, M. Götz, S. Wille, Y.K. Mishra, R. Adelung, C. Zollfrank
(See online at https://doi.org/10.1002/adma.201203849) - Fabrication of Macroscopically Flexible and Highly Porous 3D Semiconductor Networks from Interpenetrating Nanostructures by a Simple Flame Transport Approach. Particle & Particle Systems Characterization 2013, 30, 775-783
Y.K. Mishra, S. Kaps, A. Schuchardt, I. Paulowicz, X. Jin, D. Gedamu, S. Freitag, M. Claus, S. Wille, A. Kovalev, S.N. Gorb, R. Adelung
(See online at https://doi.org/10.1002/ppsc.201300197) - Formation of Self-organized Silver Nanocup-Type Structures and Their Plasmonic Absorption. Plasmonics 2013, 8, 811-815
Y.K. Mishra, R. Adelung, G. Kumar, M. Elbahri, S. Mohapatra, R. Singhal, A. Tripathi, D.K. Avasthi
(See online at https://doi.org/10.1007/s11468-013-9477-2) - Rapid Fabrication Technique for Interpenetrated ZnO Nanotetrapod Networks for Fast UV Sensors. Adv. Mater. 2013, 26, 1541-1550
D. Gedamu, I. Paulowicz, S. Kaps, O. Lupan, S. Wille, G. Haidarschin, Y. K. Mishra, R. Adelung
(See online at https://doi.org/10.1002/adma.201304363) - Spin-Crossover Complex on Au(111): Structural and Electronic Differences Between Mono- and Multilayers. Chem. Eur. J. 2013, 19, 15702-15709
T. G. Gopakumar, M. Bernien, H. Naggert, F. Matino, C.F. Hermanns, A. Bannwarth, S. Mühlenberend, A. Krüger, D. Krüger, F. Nickel, W. Walter, R. Berndt, W. Kuch, F. Tuczek
(See online at https://doi.org/10.1002/chem.201302241) - Nanocomposite Electrospun Nanofiber Membranes for Environmental Remediation. Materials 2014, 7, 1017-1045
S. Homaeigohar, M. Elbahri
(See online at https://doi.org/10.3390/ma7021017) - Highly Efficient Thermal and Light-Induced Spin-State Switching of an Fe(II) Complex in Direct Contact with a Solid Surface. ACS Nano 2015, 9, 8960-8966
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) - Photoswitchable Magnetic Resonance Imaging Contrast by Improved Light-Driven Coordination-Induced Spin State Switch. J. Am. Chem. Soc. 2015, 137, 7552–7555
M. Dommaschk, M. Peters, F. Gutzeit, C. Schütt, C. Näther, F.D. Sönnichsen, S. Tiwari, C. Riedel, S. Boretius, R. Herges
(See online at https://doi.org/10.1021/jacs.5b00929) - Switching of Bacterial Adhesion to a Glycosylated Surface by Reversible Reorientation of the Carbohydrate Ligand. Angew. Chem. Int. Ed. 2014, 53, 14583-14586
T. Weber, V. Chandrasekaran, I. Stamer, M.B. Thygesen, A. Terfort, T.K. Lindhorst
(See online at https://doi.org/10.1002/anie.201409808) - Heterodiazocines: Synthesis and Photochromic Properties, Trans to Cis Switching within the Bio-optical Window. J. Am. Chem. Soc. 2016, 138, 13111-13114
M. Hammerich, C. Schütt, C. Stähler, P. Lentes, F. Röhricht, R. Höppner, R. Herges
(See online at https://doi.org/10.1021/jacs.6b05846)
