Visualization and thermodynamic encoding of single-molecule partition function projections

Palma, Carlos‐Andres; Björk, Jonas; Klappenberger, Florian; Arras, Emmanuel; Kühne, Dirk; Stafström, Sven; Barth, Johannes V.

doi:10.1038/ncomms7210

Cited by 25 publications

(18 citation statements)

References 63 publications

(95 reference statements)

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“…A detailed calculation of non-integer stack-shifts (see Supplementary Figure S1) allows us estimating the binding energy per H⋅⋅⋅F bond of up to 30 meV (25 meV for integer-only stackshifts) for the molecules considered here. The atomic configurations that correspond to minima in the binding energy curve -with the fluorine atom being located in between two hydrogen atoms of a benzene ring or in between two phenyl groups -agree with those found for 6Pdicarbonitrile/Ag(111) 60 and also the experimentally observed stack-shifts (Figures 3b and 4b).…”

Section: Mev Including Polarization and Dispersion Via Pbe+vdw And Psupporting

confidence: 83%

Subtle Fluorination of Conjugated Molecules Enables Stable Nanoscale Assemblies on Metal Surfaces

et al. 2018

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In molecular self-assembly on surfaces, the structure is governed by the intricate balance of attractive and repulsive forces between molecules as well as between molecules and substrate. Frequently, repulsive interactions between molecules adsorbed on a metal surface dominate in the low coverage regime, and dense self-assembled structures can only be observed close to full monolayer coverage. Here we demonstrate that fluorination at selected positions of conjugated molecules provides for sufficiently strong yet non-rigid H⋅⋅⋅F bonding capability that enables (i) the formation of stable nanoscale molecular assemblies on a metal surface and (ii) steering the assemblies' structure. This approach should be generally applicable and will facilitate the construction and study of individual nanoscale molecular assemblies with structures that are not attainable in the high coverage regime.

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Section: Mev Including Polarization and Dispersion Via Pbe+vdw And Psupporting

confidence: 83%

Subtle Fluorination of Conjugated Molecules Enables Stable Nanoscale Assemblies on Metal Surfaces

et al. 2018

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“…To our knowledge, such a large area is unprecedented for homomolecular surface‐supported porphyrin‐based architectures. Consequently, the Cu‐directed TPyPP network might serve as a template to trap and order large adsorbates or even molecular aggregates . To this end, the intrinsic flexibility opens perspectives for hosting and sorting specific molecular guest species, enabling an adaptive behavior of the pores, thus representing a two‐dimensional analogue of a “soft porous crystal” .…”

Section: Resultsmentioning

confidence: 94%

Tailoring Large Pores of Porphyrin Networks on Ag(111) by Metal–Organic Coordination

Bischoff

Seufert

et al. 2016

Chemistry A European J

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The engineering of nanoarchitectures to achieve tailored properties relevant for macroscopic devices is a key motivation of organometallic surface science. To this end, understanding the role of molecular functionalities in structure formation and adatom coordination is of great importance. In this study, the differences in formation of Cu-mediated metal-organic coordination networks based on two pyridyl- and cyano-bearing free-base porphyrins on Ag(111) are elucidated by use of low-temperature scanning tunneling microscopy (STM). Distinct coordination networks evolve via different pathways upon codeposition of Cu adatoms. The cyano-terminated module directly forms 2D porous networks featuring fourfold-coordinated Cu nodes. By contrast, the pyridyl species engage in twofold coordination with Cu and a fully reticulated 2D network featuring a pore size exceeding 3 nm only evolves via an intermediate structure based on 1D coordination chains. The STM data and complementary Monte Carlo simulations reveal that these distinct network architectures originate from spatial constraints at the coordination centers. Cu adatoms are also shown to form two- and fourfold monoatomic coordination nodes with monotopic nitrogen-terminated linkers on the very same metal substrate-a versatility that is not achieved by other 3d transition metal centers but consistent with 3D coordination chemistry. This study discloses how specific molecular functionalities can be applied to tailor coordination architectures and highlights the potential of Cu as coordination center in such low-dimensional structures on surfaces.

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“…Accordingly, if the STM tip constrained the possible locations of the butyl chains of the DBS molecule (analogously to the lateral confinement of metal-organic meshes in the work of Palma et al . 27 ), then a concurrent change in entropy would follow. However, it would not a priori follow that the entropy change should compensate the enthalpy ( Fig.…”

Section: Discussionmentioning

confidence: 99%

Surface single-molecule dynamics controlled by entropy at low temperatures

et al. 2017

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Configuration transitions of individual molecules and atoms on surfaces are traditionally described using an Arrhenius equation with energy barrier and pre-exponential factor (attempt rate) parameters. Characteristic parameters can vary even for identical systems, and pre-exponential factors sometimes differ by orders of magnitude. Using low-temperature scanning tunnelling microscopy (STM) to measure an individual dibutyl sulfide molecule on Au(111), we show that the differences arise when the relative position of tip apex and molecule changes by a fraction of the molecule size. Altering the tip position on that scale modifies the transition's barrier and attempt rate in a highly correlated fashion, which results in a single-molecular enthalpy-entropy compensation. Conversely, appropriately positioning the STM tip allows selecting the operating point on the compensation line and modifying the transition rates. The results highlight the need to consider entropy in transition rates of single molecules, even at low temperatures.

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Visualization and thermodynamic encoding of single-molecule partition function projections

Cited by 25 publications

References 63 publications

Subtle Fluorination of Conjugated Molecules Enables Stable Nanoscale Assemblies on Metal Surfaces

Subtle Fluorination of Conjugated Molecules Enables Stable Nanoscale Assemblies on Metal Surfaces

Tailoring Large Pores of Porphyrin Networks on Ag(111) by Metal–Organic Coordination

Surface single-molecule dynamics controlled by entropy at low temperatures

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