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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Directed Gas-Phase Formation of Azulene (C 10 H 8 ): Unraveling the Bottom-Up Chemistry of Saddle-Shaped Aromatics

The azulene (C 10 H 8 ) molecule, the simplest polycyclic aromatic hydrocarbon (PAH) carrying a fused seven- and five-membered ring, is regarded as a fundamental molecular building block of saddle-shaped carbonaceous nanostructures such as curved nanographenes in the interstellar medium. However, an understanding of the underlying gas-phase formation mechanisms of this nonbenzenoid 10π-Hückel aromatic molecule under low-temperature conditions is in its infancy. Here, by merging crossed molecular beam experiments with electronic structure calculations and molecular dynamics simulations, our investigations unravel an unconventional low-temperature, barrierless route to azulene via the reaction of the simplest organic radical, methylidyne (CH), with indene (C 9 H 8 ) through ring expansion. This reaction might represent the initial step toward to the formation of saddle-shaped PAHs with seven-membered ring moieties in hydrocarbon-rich cold molecular clouds such as the Taurus Molecular Cloud-1 (TMC-1). These findings challenge conventional wisdom that molecular mass growth processes to nonplanar PAHs, especially those containing seven-membered rings, operate only at elevated pressure and high-temperature conditions, thus affording a versatile low-temperature route to contorted aromatics in our galaxy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Chirality Amplified: Long, Discrete Helicene Nanoribbons

Here we report the synthesis of two polyhelicene frameworks consisting, from end-to-end, of 18 and 24 fused benzene rings. The latter exhibits the largest electronic circular dichroism in the visible spectrum of any molecule. These shape-persistent helical nanoribbons incorporate multiple helicenes, a class of contorted polycyclic aromatic molecules consisting of ortho-annulated rings. These conjugated, chiral molecules have interesting chemical, biological, and chiroptical properties; however, there are very few helicenes with extraordinary chiroptical response over a broad range of the visible spectrum—a key criterion for applications such as chiral optoelectronics. In this report, we show that coupling the polyhelicene framework with multiple perylene-diimide subunits elicits a significant chiroptic response. Notably, the molar circular dichroism increases faster than the absorptivity of these molecules as their helical axis lengthens. Computational analysis reveals that the greatly amplified circular dichroism arises from exciton-like interactions between the perylene-diimide and the helicene moieties. As a result, we predict that even greater chiroptic enhancement will result from further axial elongation of these nanoribbons, which can be readily enabled via the iterative synthetic method presented herein.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Stringing the Perylene Diimide Bow

This study explores a new mode of contortion in perylene diimides where the molecule is bent, like a bow, along its long axis. These bowed PDIs were synthesized through a facile fourfold Suzuki macrocyclization with aromatic linkers and a tetraborylated perylene diimide that introduces strain and results in a bowed structure. By altering the strings of the bow, the degree of bending can be controlled from flat to highly bent. Through spectroscopy and quantum chemical calculations, it is demonstrated that the energy of the lowest unoccupied orbital can be controlled by the degree of bending in the structures and that the energy of the highest occupied orbital can be controlled to a large extent by the constitution of the aromatic linkers. The important finding is that the bowing results not only in red-shifted absorptions but also more facile reductions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Reduction of π–Expanded Cyclooctatetraene with Lithium: Stabilization of the Tetra–Anion through Internal Li + Coordination

The chemical reduction of a π-expanded polycyclic framework comprising a cyclooctatetraene moiety, octaphenyltetrabenzocyclooctatetraene, with lithium metal readily affords the corresponding tetra-anion instead of the expected aromatic dianion. As revealed by X-ray crystallography, the highly contorted tetra-anion is stabilized by coordination of two internally bound Li + , while two external cations remain solvent separated. The variable-temperature 7 Li NMR spectra in THF confirm the presence of three types of Li + ions and clearly differentiate internal binding, consistent with the crystal structure. Density-functional theory calculations suggest that the formation of the highly charged tetra-reduced carbanion is stabilized through Li + coordination under the applied experimental conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Stringing the Perylene Diimide Bow

Abstract This study explores a new mode of contortion in perylene diimides where the molecule is bent, like a bow, along its long axis. These bowed PDIs were synthesized through a facile fourfold Suzuki macrocyclization with aromatic linkers and a tetraborylated perylene diimide that introduces strain and results in a bowed structure. By altering the strings of the bow, the degree of bending can be controlled from flat to highly bent. Through spectroscopy and quantum chemical calculations, it is demonstrated that the energy of the lowest unoccupied orbital can be controlled by the degree of bending in the structures and that the energy of the highest occupied orbital can be controlled to a large extent by the constitution of the aromatic linkers. The important finding is that the bowing results not only in red‐shifted absorptions but also more facile reductions.

Liu, Taifeng↗