Mono- and multilayers of molecular spoked carbazole wheels on graphite

Jester, Stefan‐S.; Aggarwal, A. Vikas; Kalle, Daniel; Höger, Sigurd

doi:10.3762/bjoc.10.295

Cited by 6 publications

(6 citation statements)

References 16 publications

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“…Among other supramolecular interactions, host–guest complexation on 2D networks provides an interesting platform to create functional multicomponent layers 10 11 , nanostructures 12 13 and prototypical devices 14 , and establish the first step to tailor 3D architectures 15 16 . Furthermore, donor (D) - acceptor (A) complexation of common acceptor molecules into the core of giant macrocycles unveils promising building blocks for the fabrication of complex nanostructures 15 17 18 19 and self-assembled devices. The design of multifunctional organic materials containing fullerene C 60 as an active component has been extensively investigated in organic electronics 20 21 .…”

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confidence: 99%

Templated bilayer self-assembly of fully conjugated π-expanded macrocyclic oligothiophenes complexed with fullerenes

2017

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Fully conjugated macrocyclic oligothiophenes exhibit a combination of highly attractive structural, optical and electronic properties, and multifunctional molecular thin film architectures thereof are envisioned. However, control over the self-assembly of such systems becomes increasingly challenging, the more complex the target structures are. Here we show a robust self-assembly based on hierarchical non-covalent interactions. A self-assembled monolayer of hydrogen-bonded trimesic acid at the interface between an organic solution and graphite provides host-sites for the epitaxial ordering of Saturn-like complexes of fullerenes with oligothiophene macrocycles in mono- and bilayers. STM tomography verifies the formation of the templated layers. Molecular dynamics simulations corroborate the conformational stability and assign the adsorption sites of the adlayers. Scanning tunnelling spectroscopy determines their rectification characteristics. Current–voltage characteristics reveal the modification of the rectifying properties of the macrocycles by the formation of donor–acceptor complexes in a densely packed all-self-assembled supramolecular nanostructure.

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confidence: 99%

Templated bilayer self-assembly of fully conjugated π-expanded macrocyclic oligothiophenes complexed with fullerenes

2017

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“…In our previous work, we focused mainly on the structuring of the graphite surface, including homo‐ as well as coadsorptions of macrocycles, [8b] molecular spoked wheels (MSWs), [10b, 12] and also highly strained bicyclophanes with vertical extensions along the surface normal [11] . The sizes of the latter are adjustable, and the pillars at the intraannular bridges are separated up to 2 nm, although the other parts of the molecules are densely packed.…”

Section: Figurementioning

confidence: 99%

Supramolecular Nanopatterns of Molecular Spoked Wheels with Orthogonal Pillars: The Observation of a Fullerene Haze

et al. 2021

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Molecular spoked wheels with intraannular functionalizable pillars are synthesized in a modular approach. The functionalities at their ends are variable, and a propargyl alcohol, a [6,6]‐phenyl‐C61‐butyrate, and a perylene monoimide are investigated. All compounds form two‐dimensional crystals on highly oriented pyrolytic graphite at the solid–liquid interface. As determined by submolecularly resolved scanning tunneling microscopy, the pillars adopt equilibrium distances of 6.0 nm. The fullerene has a residual mobility, limited by the length of the flexible connector unit. The experimental results are supported and rationalized by molecular dynamics simulations. These also show that, in contrast, the more rigidly attached perylene monoimide units remain oriented along the surface normal and maintain a smallest distance of 2 nm above the graphite substrate. The robust packing concept also holds for cocrystals with molecular hexagons that expand the pillar–pillar distances by 15 % and block unspecific intercalation.

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“…One strategy to overcome this challenge is exploiting noncovalent interactions, such as hydrogen bonding − or metal coordination, − to guide structural preorganization. Alternatively, wire-spoked wheel-like cores are employed to bring reactive ends in close proximity to build circular architectures. ,, …”

Section: Background and Design Principlesmentioning

confidence: 99%

“…Alternatively, wire-spoked wheel-like cores are employed to bring reactive ends in close proximity to build circular architectures. 31,60,61 In the absence of such secondary interactions or auxiliary scaffolds, molecular design based on first-principles is needed to limit the number of possible conformations to be taken by the open-chain precursor L en route to the macrocyclic product M (Scheme 2). For this purpose, we decided to employ rigid structural motifs that enforce consecutive turns and allow for only a finite number of "rotatable" bonds along the molecular backbone.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Within this context, shape-persistent macrocycles emerge as ideal candidates to advance molecular design strategies and to study self-assembly on the surface. These molecules are advantageous because of key interaction points available for molecular design around the conformationally rigid backbone, − peripheral interactions to direct lateral/2D organization, − and facial interactions with a surface or to direct the formation of 3D structures. − ,,− These properties contribute to the success of many macrocycles for long-range structural ordering at surfaces.…”

Section: Introductionmentioning

confidence: 99%

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From Foldable Open Chains to Shape-Persistent Macrocycles: Synthesis, Impact on 2D Ordering, and Stimulated Self-Assembly

et al. 2018

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Small molecule self-assembly at surfaces offers an efficient route to highly ordered organic films that can be programmed for a variety of chemical and electronic applications. The success of these materials depends on the ability to program intermolecular interactions to guide precise structural ordering. Toward this objective, we have designed and synthesized a series of bis(triazolo)benzene-based π-conjugated molecules. Our synthesis exploits a last-stage C-C cross-coupling reaction to close up zigzag-shaped linear precursors to cyclized products, so that direct side-by-side comparisons can be made for their structure-dependent self-assembly behavior at surfaces and response to external stimuli. Indeed, scanning tunneling microscopy (STM) analysis revealed distinct differences as the conformational flexibility of the molecular backbone and the chemical structure of the peripheral groups are varied. Specifically, alkyl chains adsorb and form interdigitated structures, whereas oligo ethylene glycol (OEG) chains remain desorbed and thus shift self-assembly to more densely packed π-conjugated cores. While the macrocycles self-assemble immediately and spontaneously, their linear precursors exhibit slower self-assembly kinetics, which could be attributed to the difference in the degree of conformational freedom. We also found that perturbation by the STM tip and the addition of cosolutes profoundly impacted the kinetics of self-assembly and surface patterning. This highly unusual behavior highlights the importance of noncovalent interactions that are inherently weak in solution but can be made strong for symmetric and conformationally restricted molecules confined within 2D surfaces.

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Mono- and multilayers of molecular spoked carbazole wheels on graphite

Cited by 6 publications

References 16 publications

Templated bilayer self-assembly of fully conjugated π-expanded macrocyclic oligothiophenes complexed with fullerenes

Templated bilayer self-assembly of fully conjugated π-expanded macrocyclic oligothiophenes complexed with fullerenes

Supramolecular Nanopatterns of Molecular Spoked Wheels with Orthogonal Pillars: The Observation of a Fullerene Haze

From Foldable Open Chains to Shape-Persistent Macrocycles: Synthesis, Impact on 2D Ordering, and Stimulated Self-Assembly

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