Unexpected Scholl Reaction of 6,7,13,14-Tetraarylbenzo[k]tetraphene: Selective Formation of Five-Membered Rings in Polycyclic Aromatic Hydrocarbons
Cyclodehydrogenation is a versatile reaction that has enabled the syntheses of numerous polycyclic aromatic hydrocarbons (PAHs). We now describe a unique Scholl reaction of 6,7,13,14-tetraarylbenzo[k]tetraphene, which "unexpectedly" forms five-membered rings accompanying highly selective 1,2-shift of aryl groups. The geometric and optoelectronic nature of the resulting bistetracene analogue with five-membered rings is comprehensively investigated by single-crystal X-ray, NMR, UV-vis absorption, and cyclic voltammetry analyses. Furthermore, a possible mechanism is proposed to account for the selective five-membered-ring formation with the rearrangement of the aryl groups, which can be ration…
Fused Dibenzo[ a , m ]rubicene: A New Bowl-Shaped Subunit of C 70 Containing Two Pentagons
Total synthetic approaches of fullerenes are the holy grail for organic chemistry. So far, the main attempts have focused on the synthesis of the buckminsterfullerene C60. In contrast, access to subunits of the homologue C70 remains challenging. Here, we demonstrate an efficient bottom-up strategy toward a novel bowl-shaped polycyclic aromatic hydrocarbons (PAH) C34 with two pentagons. This PAH represents a subunit for C70 and of other higher fullerenes. The bowl-shaped structure was unambiguously determined by X-ray crystallography. A bowl-to-bowl inversion for a C70 fragment in solution was investigated by dynamic NMR analysis, showing a bowl-to-bowl inversion energy (ΔG(⧧)) of 16.7 kcal …
Free-Standing Mono layer Two-Dimensional Supramolecular Organic Framework with Good Internal Order
Utilizing dynamic self-assembly and self-sorting to obtain large-area, molecularly precise monolayered structures represents a promising approach toward two-dimensional supramolecular organic frameworks (2D SOF) or 2D supramolecular polymers. So far, related approaches suffer from small domain sizes, fragility and weak long-range internal order. Here we report on the self-assembly of a host-guest enhanced donor-acceptor interaction, consisting of a tris(methoxynaphthyl)-substituted truxene spacer, and a naphthalene diimide substituted with N-methyl viologenyl moieties as donor and acceptor monomers, respectively, in combination with cucurbit[8]uril as host monomer toward monolayers of an un…
Polycyclic aromatic chains on metals and insulating layers by repetitive [3+2] cycloadditions
The vast potential of organic materials for electronic, optoelectronic and spintronic devices entails substantial interest in the fabrication of π-conjugated systems with tailored functionality directly at insulating interfaces. On-surface fabrication of such materials on non-metal surfaces remains to be demonstrated with high yield and selectivity. Here we present the synthesis of polyaromatic chains on metallic substrates, insulating layers, and in the solid state. Scanning probe microscopy shows the formation of azaullazine repeating units on Au(111), Ag(111), and h-BN/Cu(111), stemming from intermolecular homo-coupling via cycloaddition reactions of CN-substituted polycyclic aromatic az…
Oligophenyls with Multiple Disulfide Bridges as Higher Homologues of Dibenzo[c,e][1,2]dithiin: Synthesis and Application in Lithium-Ion Batteries.
Abstract Higher homologues of dibenzo[c,e][1,2]dithiin were synthesized from oligophenyls bearing multiple methylthio groups. Single‐crystal X‐ray analyses revealed their nonplanar structures and helical enantiomers of higher meta‐congener 6. Such dibenzo[1,2]dithiin homologues are demonstrated to be applicable to lithium‐ion batteries as cathode, displaying a high capacity of 118 mAh g−1 at a current density of 50 mA g−1.
A simple approach towards one-dimensional mesoporous carbon with superior electrochemical capacitive activity.
One-dimensional (1D) mesoporous carbons with highly ordered 3D interconnected pore structure and large-diameter pore size (10–20 nm) have been synthesized by a simple precursor-controlled thermolysis approach; such unique carbonaceous frameworks show superior capacitive behavior in electrochemical double-layer capacitors.
Chemical Vapor Deposition Synthesis and Terahertz Photoconductivity of Low-Band-Gap N = 9 Armchair Graphene Nanoribbons.
Recent advances in bottom-up synthesis of atomically defined graphene nanoribbons (GNRs) with various microstructures and properties have demonstrated their promise in electronic and optoelectronic devices. Here we synthesized N = 9 armchair graphene nanoribbons (9-AGNRs) with a low optical band gap of ∼1.0 eV and extended absorption into the infrared range by an efficient chemical vapor deposition process. Time-resolved terahertz spectroscopy was employed to characterize the photoconductivity in 9-AGNRs and revealed their high intrinsic charge-carrier mobility of approximately 350 cm2·V-1·s-1.
Synthesis of Microporous Carbon Nanofibers and Nanotubes from Conjugated Polymer Network and Evaluation in Electrochemical Capacitor
One-dimensional fibers and tubes are constructed through the oriented carbon-carbon cross-linking reactions towards rigid conjugated polymer networks. As the result, a template-free and one-step synthesis of CNTs and CNFs is achieved through a simple carbonization of the as-formed carbon-rich tubular and fiberlike polyphenylene precursors under argon. Microporous CNTs and CNFs with a surface area up to 900 m2 g–1 are obtained, together with HR-TEM characterizations indicating the formation of intrinsic microporous structure in these rigid carbon-rich networks. The primary electrochemical experiments reveal their promising applications as advanced electrodes in electrochemical double-layered…
Fabrication of cobalt and cobalt oxide/graphene composites: towards high-performance anode materials for lithium ion batteries.
Robust Two-Dimensional Electronic Properties in Three-Dimensional Microstructures of Rotationally Stacked Turbostratic Graphene
We report on the electronic properties of turbostratic graphitic microdisks, rotationally stacked systems of graphene layers, where interlayer twisting leads to electronic decoupling resulting in charge-transport properties that retain the two dimensionality of graphene, despite the presence of a large number of layers. A key fingerprint of this reduced dimensionality is the effect of weak charge-carrier localization that we observe at low temperatures. The disks' resistivity measured as a function of magnetic field changes its shape from parabolic at room temperature to linear at a temperature of 2.7 K indicating further this type of two-dimensional transport. Compared to Bernal stacked gr…
Composites of Graphene with Large Aromatic Molecules
Turbostratic graphitic microstructures: electronically decoupled multilayer graphene devices with robust high charge carrier mobility
Carbon nanomaterials continue to amaze scientists due to their exceptional physical properties. Recently there have been theoretical predictions and first reports on graphene multilayers, where, due to the rotation of the stacked layers, outstanding electronic properties are retained while the susceptibility to degradation and mechanical stress is strongly reduced due to the multilayer nature. Here we show that fully turbostratic multilayer graphitic microstructures combine the high charge carrier mobilities necessary for advanced electronic and spintronic devices with the robustness of graphitic structures. Structural characterization of disk-shaped graphitic microstructures using Raman sp…
Synthesis of Graphene Nanoribbons by Ambient-Pressure Chemical Vapor Deposition and Device Integration
Graphene nanoribbons (GNRs), quasi-one-dimensional graphene strips, have shown great potential for nanoscale electronics, optoelectronics, and photonics. Atomically precise GNRs can be "bottom-up" synthesized by surface-assisted assembly of molecular building blocks under ultra-high-vacuum conditions. However, large-scale and efficient synthesis of such GNRs at low cost remains a significant challenge. Here we report an efficient "bottom-up" chemical vapor deposition (CVD) process for inexpensive and high-throughput growth of structurally defined GNRs with varying structures under ambient-pressure conditions. The high quality of our CVD-grown GNRs is validated by a combination of different …
Lateral Fusion of Chemical Vapor Deposited N = 5 Armchair Graphene Nanoribbons
Bottom-up synthesis of low-bandgap graphene nanoribbons with various widths is of great importance for their applications in electronic and optoelectronic devices. Here we demonstrate a synthesis of N = 5 armchair graphene nanoribbons (5-AGNRs) and their lateral fusion into wider AGNRs, by a chemical vapor deposition method. The efficient formation of 10- and 15- AGNRs is revealed by a combination of different spectroscopic methods, including Raman and UV−visnear-infrared spectroscopy as well as by scanning tunneling microscopy. The degree of fusion and thus the optical and electronic properties of the resulting GNRs can be controlled by the annealing temperature, providing GNR films with o…
On-surface Synthesis of a Chiral Graphene Nanoribbon with Mixed Edge Structure.
Abstract Chiral graphene nanoribbons represent an important class of graphene nanomaterials with varying combinations of armchair and zigzag edges conferring them unique structure‐dependent electronic properties. Here, we describe the on‐surface synthesis of an unprecedented cove‐edge chiral GNR with a benzo‐fused backbone on a Au(111) surface using 2,6‐dibromo‐1,5‐diphenylnaphthalene as precursor. The initial precursor self‐assembly and the formation of the chiral GNRs upon annealing are revealed, along with a relatively small electronic bandgap of approximately 1.6 eV, by scanning tunnelling microscopy and spectroscopy.
CCDC 1910693: Experimental Crystal Structure Determination
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