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Exploring a Route to Cyclic Acenes by On-Surface Synthesis.

ABSTRACT: A route to generate cyclacenes by on-surface synthesis is explored. We started by synthesizing two tetraepoxycyclacenes by sequences of Diels-Alder cycloadditions. Subsequently, these molecules were deposited onto Cu(111) and scanning-tunneling-microscopy(STM)-based atom manipulation was employed to dissociate the oxygen atoms. Atomic force microscopy (AFM) with CO-functionalized tips enabled the detailed characterization of the reaction products and revealed that, at most, two oxygens per molecule could be removed. Importantly, our experimental results suggest that the generation of cyclacenes by the described route might be possible for larger epoxycyclacenes.

SUBMITTER: Schulz F

PROVIDER: S-EPMC6618096 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Unilaterally Fluorinated Acenes: Synthesis and Solid-State Properties.

Project description:The rapid development of organic electronics is closely related to the availability of molecular materials with specific electronic properties. Here, we introduce a novel synthetic route enabling a unilateral functionalization of acenes along their long side, which is demonstrated by the synthesis of 1,2,10,11,12,14-hexafluoropentacene (1) and the related 1,2,9,10,11-pentafluorotetracene (2). Quantum chemical DFT calculations in combination with optical and X-ray absorption spectroscopy data indicate that the single-molecule properties of 1 are a connecting link between the organic semiconductor model systems pentacene (PEN) and perfluoropentacene (PFP). In contrast, the crystal structure analysis reveals a different packing motif than for the parent molecules. This can be related to distinct F⋅⋅⋅H interactions identified in the corresponding Hirshfeld surface analysis and also affects solid-state properties such as the exciton binding energy and the sublimation enthalpy.

| S-EPMC7540388 | biostudies-literature

Higher Acenes by On-Surface Dehydrogenation: From Heptacene to Undecacene.

Project description:A unified approach to the synthesis of the series of higher acenes up to previously unreported undecacene has been developed through the on-surface dehydrogenation of partially saturated precursors. These molecules could be converted into the parent acenes by both atomic manipulation with the tip of a scanning tunneling and atomic force microscope (STM/AFM) as well as by on-surface annealing. The structure of the generated acenes has been visualized by high-resolution non-contact AFM imaging and the evolution of the transport gap with the increase of the number of fused benzene rings has been determined on the basis of scanning tunneling spectroscopy (STS) measurements.

| S-EPMC6099251 | biostudies-literature

Synthesis of cyclic alkenylsiloxanes by semihydrogenation: a stereospecific route to (Z)-alkenyl polyenes.

Project description:Cyclic alkenylsiloxanes were synthesized by semihydrogenation of alkynylsilanes-a reaction previously plagued by poor stereoselectivity. The silanes, which can be synthesized on multigram scale, undergo Hiyama-Denmark coupling to give (Z)-alkenyl polyene motifs found in bioactive natural products. The ring size of the silane is crucial: five-membered cyclic siloxanes also couple under fluoride-free conditions, whilst their six-membered homologues do not, enabling orthogonality within this structural motif.

| S-EPMC4531823 | biostudies-literature

The Cyclic Nitronate Route to Pharmaceutical Molecules: Synthesis of GSK's Potent PDE4 Inhibitor as a Case Study.

Project description:An efficient asymmetric synthesis of GlaxoSmithKline's potent PDE4 inhibitor was accomplished in eight steps from a catechol-derived nitroalkene. The key intermediate (3-acyloxymethyl-substituted 1,2-oxazine) was prepared in a straightforward manner by tandem acylation/(3,3)-sigmatropic rearrangement of the corresponding 1,2-oxazine-N-oxide. The latter was assembled by a (4 + 2)-cycloaddition between the suitably substituted nitroalkene and vinyl ether. Facile acetal epimerization at the C-6 position in 1,2-oxazine ring was observed in the course of reduction with NaBH3CN in AcOH. Density functional theory (DFT) calculations suggest that the epimerization may proceed through an unusual tricyclic oxazolo(1,2)oxazinium cation formed via double anchimeric assistance from a distant acyloxy group and the nitrogen atom of the 1,2-oxazine ring.

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On-surface light-induced generation of higher acenes and elucidation of their open-shell character.

Project description:Acenes are an important class of polycyclic aromatic hydrocarbons which have recently gained exceptional attention due to their potential as functional organic semiconductors. Fundamentally, they are important systems to study the convergence of physico-chemical properties of all-carbon sp2-frameworks in the one-dimensional limit; and by virtue of having a zigzag edge topology they also provide a fertile playground to explore magnetism in graphenic nanostructures. The study of larger acenes is thus imperative from both a fundamental and applied perspective, but their synthesis via traditional solution-chemistry route is hindered by their poor solubility and high reactivity. Here, we demonstrate the on-surface formation of heptacene and nonacene, via visible-light-induced photo-dissociation of α-bisdiketone precursors on an Au(111) substrate under ultra-high vacuum conditions. Through combined scanning tunneling microscopy/spectroscopy and non-contact atomic force microscopy investigations, together with state-of-the-art first principles calculations, we provide insight into the chemical and electronic structure of these elusive compounds.

| S-EPMC6382834 | biostudies-literature

The Route from the Folded to the Amyloid State: Exploring the Potential Energy Surface of a Drug-Like Miniprotein.

Project description:The amyloid formation of the folded segment of a variant of Exenatide (a marketed drug for type-2 diabetes mellitus) was studied by electronic circular dichroism (ECD) and NMR spectroscopy. We found that the optimum temperature for E5 protein amyloidosis coincides with body temperature and requires well below physiological salt concentration. Decomposition of the ECD spectra and its barycentric representation on the folded-unfolded-amyloid potential energy surface allowed us to monitor the full range of molecular transformation of amyloidogenesis. We identified points of no return (e.g.; T=37?°C, pH?4.1, cE5 =250??m, cNaCl =50?mm, t>4-6?h) that will inevitably gravitate into the amyloid state. The strong B-type far ultraviolet (FUV)-ECD spectra and an unexpectedly strong near ultraviolet (NUV)-ECD signal (??275-285 ? nm ) indicate that the amyloid phase of E5 is built from monomers of quasi-elongated backbone structure (??-145°, ??+145°) with strong interstrand Tyr?Trp interaction. Misfolded intermediates and the buildup of "toxic" early-stage oligomers leading to self-association were identified and monitored as a function of time. Results indicate that the amyloid transition is triggered by subtle misfolding of the ?-helix, exposing aromatic and hydrophobic side chains that may provide the first centers for an intermolecular reorganization. These initial clusters provide the spatial closeness and sufficient time for a transition to the ?-structured amyloid nucleus, thus the process follows a nucleated growth mechanism.

| S-EPMC7028080 | biostudies-literature

Efficient route to C2 symmetric heterocyclic backbone modified cyclic peptides.

Project description:[reaction: see text] A tandem dimerization-macrocyclization approach using 1,3-dipolar azide-alkyne cycloaddition reactions has been employed in the facile and convergent solution phase syntheses of C2 symmetric cyclic peptide scaffolds bearing triazole epsilon2-amino acids as dipeptide surrogates.

| S-EPMC1829324 | biostudies-literature

A novel route to cyclic dominance in voluntary social dilemmas.

Project description:Cooperation is the backbone of modern human societies, making it a priority to understand how successful cooperation-sustaining mechanisms operate. Cyclic dominance, a non-transitive set-up comprising at least three strategies wherein the first strategy overrules the second, which overrules the third, which, in turn, overrules the first strategy, is known to maintain biodiversity, drive competition between bacterial strains, and preserve cooperation in social dilemmas. Here, we present a novel route to cyclic dominance in voluntary social dilemmas by adding to the traditional mix of cooperators, defectors and loners, a fourth player type, risk-averse hedgers, who enact tit-for-tat upon paying a hedging cost to avoid being exploited. When this cost is sufficiently small, cooperators, defectors and hedgers enter a loop of cyclic dominance that preserves cooperation even under the most adverse conditions. By contrast, when the hedging cost is large, hedgers disappear, consequently reverting to the traditional interplay of cooperators, defectors, and loners. In the interim region of hedging costs, complex evolutionary dynamics ensues, prompting transitions between states with two, three or four competing strategies. Our results thus reveal that voluntary participation is but one pathway to sustained cooperation via cyclic dominance.

| S-EPMC7115231 | biostudies-literature

Bending versus Twisting Acenes - A Computational Study.

Project description:Polycyclic aromatic hydrocarbons (PAHs) are widely used in organic electronic devices. The electronic, magnetic, and optical properties of PAHs can be tuned by structural modifications to the aromatic backbone to introduce an inherent distortion from planarity, such as bending or twisting. However, it remains difficult to isolate and control the effects of such distortions. Here, we sought to understand how backbone twisting and bending affect the electronic properties of acenes, as models for larger PAHs. We found that, even when highly distorted from planarity (30° per ring), acenes maintain their aromatic character and π orbital delocalization with minor mixing of the σ and π orbitals. In addition, the energy gap between the HOMO and LUMO decreases with increasing twist, while the gap is hardly affected by bending, since the energy of both orbitals increase to a similar extent. For bent acenes in the triplet state, the spin becomes more localized with increasing bend, whereas twisting produces an evenly distributed spin delocalization. These findings can guide the synthesis of PAHs with tailored properties.

| S-EPMC8597036 | biostudies-literature

Exploring C-F···π Interactions: Synthesis, Characterization, and Surface Analysis of Copper β-Diketone Complexes.

Project description:Synthesis and characterization of two novel copper β-diketone complexes, where halogen bonds play a pivotal role in shaping their multifaceted structural landscape, have been done in the present study. This study employs X-ray diffraction, ultraviolet-visible (UV-vis) spectroscopy, and infrared (IR) spectroscopy to investigate two copper β-diketone complexes, [Cu(L1)2(ttfa)2]·2CH3OH (1) and [Cu(L1)(dfpb)2] (2), where Httfa is 4,4,4-trifluoro-1-(thiophen-2-yl)butan-3,1-dione and Hdfpb is 4,4-difluoro-1-phenylbutane-1,3-dione. Complex 1 displays a halogen bond, which contributes to its uniqueness. The coordination sphere around the copper atoms was found to be octahedral for complex 1 and pyramid with a square base for complex 2. The study also extensively discusses the interactions present in these complexes. Hirshfeld surface analysis was employed to gain a more detailed understanding of these interactions, and the results showed that hydrogen-bond interactions contributed above 30% of the whole surface area in both complexes. Additionally, the halogen bond in complex 1 was found to contribute approximately 8% of the surface. Overall, this study provides valuable insights into the structural properties and interactions of copper β-diketone complexes, which could have potential applications in various fields.

| S-EPMC10851358 | biostudies-literature

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