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Research Highlights: 2014


T. Kumagai, F. Hanke, S. Gawinkowski, J. Sharp, K. Kotsis, J. Waluk, M. Persson, and L. Grill

Controlling intramolecular hydrogen transfer by single atoms and molecules

Nature Chemistry 6, 41 (2014)

Abstract. Although the local environment of a molecule can play an important role in its chemistry, rarely has it been examined experimentally at the level of individual molecules. Here we report the precise control of intramolecular hydrogen-transfer (tautomerization) reactions in single molecules using scanning tunnelling microscopy. By placing, with atomic precision, a copper adatom close to a porphycene molecule, we found that the tautomerization rates could be tuned up and down in a controlled fashion, surprisingly also at rather large separations. Furthermore, we extended our study to molecular assemblies in which even the arrangement of the pyrrolic hydrogen atoms in the neighbouring molecule influences the tautomerization reaction in a given porphycene, with positive and negative cooperativity effects. Our results highlight the importance of controlling the environment of molecules with atomic precision and demonstrate the potential to regulate processes that occur in a single molecule.



Z. Yang, M. Corso, R. Robles, C. Lotze, R. Fitzner, E. Mena-Osteritz, P. Bäuerle, K. J. Franke, and J. I. Pascual

Orbital Redistribution in Molecular Nanostructures Mediated by Metal-Organic Bonds

ACS Nano 8, 10715 (2014)

Abstract. Dicyanovinyl-quinquethiophene (DCV5T-Me2) is a prototype conjugated oligomer for highly efficient organic solar cells. This class of oligothiophenes are built up by an electron-rich donor (D) backbone and terminal electron-deficient acceptor (A) moieties. Here, we investigated its structural and electronic properties when it is adsorbed on a Au(111) surface using low temperature scanning tunneling microscopy/spectroscopy (STM/ST.S) and atomic force microscopy (AFM). We find that DCV5T-Me2 self-assembles in extended chains, stabilized by intercalated Au atoms. The effect of metal–ligand hybridization with Au adatoms causes an energetic downshift of the DCV5T-Me2 lowest unoccupied molecular orbital (LUMO) with respect to the uncoordinated molecules on the surface. The asymmetric coordination of a gold atom to only one molecular end group leads to an asymmetric localization of the LUMO and LUMO+1 states at opposite sides. Using model density functional theory (DFT) calculations, we explain such orbital reshaping as a consequence of linear combinations of the original LUMO and LUMO+1 orbitals, mixed by the attachment of a bridging Au adatom. Our study shows that the alignment of molecular orbitals and their distribution within individual molecules can be modified by contacting them to metal atoms in specific sites.



R. Göstl and S. Hecht

Controlling Covalent Connection and Disconnection by Light

Angew. Chem. Int. Ed. 53, 8784 (2014)

Abstract. The on-going need for feature miniaturization and the growing complexity of structures for use in nanotechnology demand the precise and controlled formation of covalent bonds at the molecular level. Such control requires the use of external stimuli that offer outstanding spatial, temporal, as well as energetic resolution. Thus, photoaddressable switches are excellent candidates for creating a system that allows reversible photocontrol over covalent chemical connection and disconnection. Here we show that the formation of covalent bonds between two reagents and their scission in the resulting product can be controlled exclusively by illumination with differently colored light. A furyl-substituted photoswitchable diarylethene was shown to undergo a reversible Diels–Alder reaction with maleimide to afford the corresponding Diels–Alder adduct. Our system is potentially applicable in any field already relying on the benefits of reversible Diels–Alder reactions.



C. L. Lee, T. Liebig, S. Hecht, D. Bléger, and J. P. Rabe

Light-Induced Contraction and Extension of Single Macromolecules on a Modified Graphite Surface

ACS Nano 8, 11987 (2014)

highlighted in Perspective by P. K. Kundu and R. Klajn: "Watching Single Molecules Move in Response to Light", ACS Nano 8, 11913 (2014) (DOI:10.1021/nn506656r)

Abstract. Synthetic rigid-rod polymers incorporating multiple azobenzene photoswitches in the backbone were deposited from solution onto a monolayer of octadecylamine covering the basal plane of graphite. Large contractions and extensions of the single macromolecules on the surface were induced by irradiation with UV and visible light, respectively, as visualized by scanning force microscopy. Upon contraction, the single polymer chains form more compact nanostructures and also may move across the surface, resembling a crawling movement. We attribute the efficiency of these processes to the low mechanical and electronic coupling between the surface and polymers, the high density of azobenzenes in their backbones, and their rigidity, allowing for maximized photodeformations. The visualization of on-surface motions of single macromolecules directly induced by light, as reported herein, could help promote the development of optomechanical nanosystems.


A. Benyamini, A. Hamo, S. Viola Kusminskiy, F. von Oppen, and S. Ilani

Real-Space Tailoring of the Electron-Phonon Coupling in Ultra-Clean Nanotube Mechanical Resonators

Nature Physics 10, 151 (2014)

Abstract. The coupling between electrons and phonons is at the heart of many fundamental phenomena in nature. Despite tremendous advances in controlling electrons or phonons in engineered nanosystems, control over their coupling is still widely lacking. Here we demonstrate the ability to fully tailor electron–phonon interactions using a new class of suspended carbon nanotube devices, in which we can form highly tunable single and double quantum dots at arbitrary locations along a nanotube mechanical resonator. We find that electron–phonon coupling can be turned on and off by controlling the position of a quantum dot along the resonator. Using double quantum dots we structure the interactions in real space to couple specific electronic and phononic modes. This tailored coupling allows measurement of the phonons’ spatial parity and imaging of their mode shapes. Finally, we demonstrate coupling between phonons and internal electrons in an isolated system, decoupled from the random environment of the electronic leads, a crucial step towards fully engineered quantum-coherent electron–phonon systems.


F. Kadi, T. Winzer, E. Malic, A. Knorr, M. Mittendorff, S. Winnerl, F. Goettfert, and M. Helm

Microscopic description of intraband absorption in graphene: the occurrence of transient negative differential transmission

Phys. Rev. Lett. 113, 035502 (2014)

Abstract. We present a microscopic explanation of the controversially discussed transient negative differential transmission observed in degenerate optical pump-probe measurements in graphene. Our approach is based on the density matrix formalism allowing a time- and momentum-resolved study of carrier-light, carrier-carrier, and carrier-phonon interaction on microscopic footing. We show that phonon-assisted optical intraband transitions give rise to transient absorption in the optically excited hot carrier system counteracting pure absorption bleaching of interband transitions. While interband transition bleaching is relevant in the first hundreds of fs after the excitation, intraband absorption sets in at later times. In particular, in the low excitation regime, these intraband absorption processes prevail over the absorption bleaching resulting in a zero crossing of the differential transmission. Our findings are in good qualitative agreement with recent experimental pump-probe studies.


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