A surface-anchored molecular four-level conductance switch based on single proton transfer

Auwärter, Willi; Seufert, Knud; Bischoff, Felix; Écija, David; Vijayaraghavan, Saranyan; Joshi, Sushobhan; Klappenberger, Florian; Samudrala, Niveditha; Barth, Johannes V.

doi:10.1038/nnano.2011.211

Cited by 260 publications

(356 citation statements)

References 34 publications

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“…More broadly, strategies within the past decade to combine memristive 21,26 and spintronic 15 functionalities in devices have relied on extrinsic 27,28 or nominally intrinsic 29 properties of the materials and interfaces within the device. Similar yet separated memristive 2 and spintronic 11 functionalities have arisen in the ultimate limit of single-molecule junctions.…”

Section: Discussionmentioning

confidence: 99%

Robust spin crossover and memristance across a single molecule

et al. 2012

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A nanoscale molecular switch can be used to store information in a single molecule. Although the switching process can be detected electrically in the form of a change in the molecule′s conductance, adding spin functionality to molecular switches is a key concept for realizing molecular spintronic devices. Here we show that iron-based spin-crossover molecules can be individually and reproducibly switched between a combined high-spin, high-conduction state and a low-spin, low-conduction state, provided the individual molecule is decoupled from a metallic substrate by a thin insulating layer. These results represent a step to achieving combined spin and conduction switching functionality on the level of individual molecules.

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Section: Discussionmentioning

confidence: 99%

Robust spin crossover and memristance across a single molecule

et al. 2012

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“…7 On this route, the recently discovered topological insulators (TI) represent a promising new class of materials. 8,9 TIs are insulating in the bulk but conductive on their surface, where they host linearly dispersing Dirac fermions protected by time-reversal symmetry.…”

Section: Introductionmentioning

confidence: 99%

Probing the Electronic Properties of Individual MnPc Molecules Coupled to Topological States

et al. 2014

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Hybrid organic/inorganic interfaces have been widely reported to host emergent properties that go beyond those of their single constituents. Coupling molecules to the recently discovered topological insulators, which possess a linearly dispersing and spin-momentum-locked Dirac fermions, may offer a promising platform towards new functionalities. Here, we report a scanning tunneling microscopy and spectroscopy study of the prototypical interface between MnPc molecules and a Bi 2 Te 3 surface. MnPc is found to bind stably to the substrate through its central Mn atom. The adsorption process is only accompanied with a minor charge transfer across the interface, resulting in a moderately n-doped Bi 2 Te 3 surface. More remarkably, topological states remain completely unaffected by the presence of the molecules, as evidenced by the absence of scattering patterns around adsorption sites. Interestingly, we show that, while the HOMO and LUMO orbitals closely resembles those of MnPc in the gas phase, a new hybrid states emerges through interaction with the substrate. Our results pave the way towards hybrid organic-topological insulator heterostructures, which may unveil a broad range of exciting and unknown phenomena.2

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“…[10][11][12][13][14][15] The enormous potential of porphyrins for the fabrication of tailor-made functional molecular architectures on well-defined substrates has stimulated significant activities in fundamental research. 4,[16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] In this contribution, we review recent advances in the understanding of the dynamic behaviour of porphyrins, as representatives of organic molecules, adsorbed on a Cu(111) single crystal surface in ultra-high vacuum (UHV). Based on temperaturedependent measurements of individual molecules, the kinetics and energetics of diffusion 33,34 and rotation, 34 of the so-called self-metalation reaction 35,36 and finally of conformational switching of particular free base porphyrins 37 can be determined.…”

Section: Introductionmentioning

confidence: 99%

Studying the dynamic behaviour of porphyrins as prototype functional molecules by scanning tunnelling microscopy close to room temperature

Marbach

Steinrück

2014

Chem. Commun.

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Scanning tunnelling microscopy (STM) enables us to directly observe the dynamic behaviour of organic molecules on surfaces. While imaging atoms and molecules using STM is certainly fascinating by itself, corresponding temperature-dependent measurements allow for the quantitative determination of the energetics and kinetics of the underlying molecular surface processes. Herein, we review recent advances in the STM investigation of the dynamic behaviour of adsorbed porphyrins at and close to room temperature.Three different case studies are discussed, providing insight into the dynamics of diffusion, rotation, reaction, and molecular switching at surfaces, based on isothermal STM measurements. The reviewed examples demonstrate that variable temperature STM can be a suitable tool to directly monitor the dynamic behaviour of individual adsorbed molecules, at and close to room temperature. Free base porphyrins on Cu(111) proved to be particularly suitable for these studies due to the strong bonding interaction between the iminic nitrogen atoms in the porphyrin macrocycle and the Cu substrate atoms. As a consequence, the corresponding activation energies for surface diffusion, self-metalation reaction and conformational switching are of a magnitude that allows for monitoring the processes at and around room temperature, in contrast to most previous studies, which were performed at cryogenic temperatures. The kinetic analysis of the surface diffusion and self-metalation was performed using an Arrhenius approach, yielding the corresponding activation energies and preexponential factors. In contrast, the conformational switching process was analysed in the framework of transition state theory, based on the Eyring equation. This approach provides a more detailed insight into interpretable thermodynamic potentials, i.e., the enthalpic and entropic contributions to the activation barrier. The analysis shows that at room temperature the adsorption and switching behaviour of the investigated free base porphyrin on Cu(111) is dominated by entropic effects. Since the entropic energy contribution vanishes at low temperatures, the importance of experiments conducted at temperatures close to room temperature is emphasized.

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A surface-anchored molecular four-level conductance switch based on single proton transfer

Cited by 260 publications

References 34 publications

Robust spin crossover and memristance across a single molecule

Robust spin crossover and memristance across a single molecule

Probing the Electronic Properties of Individual MnPc Molecules Coupled to Topological States

Studying the dynamic behaviour of porphyrins as prototype functional molecules by scanning tunnelling microscopy close to room temperature

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