Mechanical compression in cofacial porphyrin cyclophane pincers

Hsu, Chunwei; Schosser, Werner M.; Zwick, Patrick; Dulić, Diana; Mayor, Marcel; Pauly, Fabian; Zant, Herre S. J. van der

doi:10.1039/d2sc00937d

Cited by 11 publications

(8 citation statements)

References 37 publications

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“…Non‐racemizable enantiopure organic molecule able to modify its three‐dimensional structure as a result of an applied electro‐mechanical stimulus seems to be the best candidate for these kind of studies. That is, a single chiral molecule could, in principle, adopt different chiral conformations which may also be controlled by a mechanical process [2, 20b–c] . In this sense, we recently described new fully conjugated and enantiopure helical architectures based on ortho ‐oligophenylenethynylenes ( o ‐OPEs) including a novel control of their chirality [22] .…”

Section: Introductionmentioning

confidence: 99%

Chiral Single‐Molecule Potentiometers Based on Stapled ortho‐ Oligo(phenylene)ethynylenes

et al. 2023

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We report on the chemical design of chiral molecular junctions with stress-dependent conductance, whose helicity is maintained during the stretching of a single molecule junction due to the stapling of both ends of the inner helix. In the reported compounds, different conductive pathways are observed, with clearly different conductance values and plateau-length distributions, attributed to different conformations of the helical structures. The large chiro-optical responses and the potential use of these molecules as unimolecular spin filters have been theoretically proved using state-of-theart Density Functional Theory (DFT) calculations, including a fully ab-initio estimation of the CISSoriginating spin polarization which is done, for the first time, for a realistic molecular system.

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Section: Introductionmentioning

confidence: 99%

Chiral Single‐Molecule Potentiometers Based on Stapled ortho‐ Oligo(phenylene)ethynylenes

et al. 2023

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“…For a molecular junction with vacuum boundary conditions, the calculation of transport coefficients involves a pair of metallic clusters that approximate semi-infinite electrodes (see ref. 1 and 8–10 for examples). The computed transport coefficients depend on the cluster sizes and this dependence must be extrapolated (see ref.…”

Section: Introductionmentioning

confidence: 99%

Widening of the fundamental gap in cluster GW for metal–molecular interfaces

Marek,

Korytár

2024

Phys. Chem. Chem. Phys.

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“…16 One approach to achieve this conformational control is to incorporate intramolecular interactions such as π-stacking and hydrogen bonding into the single-molecule backbone. 17 This gap in the literature can be ascribed to the fact that most single-molecule wires with flexible σ-backbones have conformations that are overwhelmingly influenced by steric effects (Figure 1a). Though alkane wires are freely rotating, their backbones predominately exist in anti (ω = 180°) dihedral geometries due to repulsive steric crowding in their gauche (ω = 60°) conformations.…”

Section: ■ Introductionmentioning

confidence: 99%

Intramolecular London Dispersion Interactions in Single-Molecule Junctions

Hight,

Wong,

Pimentel

et al. 2024

J. Am. Chem. Soc.

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This work shows the first example of using intramolecular London dispersion interactions to control molecular geometry and quantum transport in single-molecule junctions. Flexible σ-bonded molecular junctions typically occupy straightchain geometries due to steric effects. Here, we synthesize a series of thiomethyl-terminated oligo(dimethylsilmethylene)s that bear [CH 2 −Si(CH 3 ) 2 ] n repeat units, where all backbone dihedral states are sterically equivalent. Scanning tunneling microscopy breakjunction (STM-BJ) measurements and theoretical calculations indicate that in the absence of a strong steric bias concerted intramolecular London dispersion interactions staple the carbosilane backbone into coiled conformations that remain intact even as the junction is stretched to its breakpoint. As these kinked conformations are highly resistive to electronic transport, we observe record-high conductance decay values on an experimental junction length basis (β = 1.86 ± 0.12 Å −1 ). These studies reveal the potential of using intramolecular London dispersion interactions to design single-molecule electronics.

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Mechanical compression in cofacial porphyrin cyclophane pincers

Abstract: Intra- and intermolecular interactions are dominating chemical processes, and their concerted interplay enables complex nonequilibrium states like life. While the responsible basic forces are typically investigated spectroscopically, a conductance measurement...

Cited by 11 publications

References 37 publications

Chiral Single‐Molecule Potentiometers Based on Stapled ortho‐ Oligo(phenylene)ethynylenes

Chiral Single‐Molecule Potentiometers Based on Stapled ortho‐ Oligo(phenylene)ethynylenes

Widening of the fundamental gap in cluster GW for metal–molecular interfaces

Intramolecular London Dispersion Interactions in Single-Molecule Junctions

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