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Abstract: Polycyclic aromatic hydrocarbons (PAHs) represent the link between resonance‐stabilized free radicals and carbonaceous nanoparticles generated in incomplete combustion processes and in circumstellar envelopes of carbon rich asymptotic giant branch (AGB) stars. Although these PAHs resemble building blocks of complex carbonaceous nanostructures, their fundamental formation mechanisms have remained elusive. By exploring these reaction mechanisms of the phenyl radical with biphenyl/naphthalene theoretically and experimentally, we provide compelling evidence on a novel phenyl‐addition/dehydrocyclization (PAC) pathway leading to prototype PAHs: triphenylene and fluoranthene. PAC operates efficiently at high temperatures leading through rapid molecular mass growth processes to complex aromatic structures, which are difficult to synthesize by traditional pathways such as hydrogen‐abstraction/acetylene‐addition. The elucidation of the fundamental reactions leading to PAHs is necessary to facilitate an understanding of the origin and evolution of the molecular universe and of carbon in our galaxy.

The simplest polycyclic aromatic hydrocarbon (PAH) carrying a five‐membered ring—9H‐fluorene (C13H10)—is produced isomer‐specifically in the gas phase by reacting benzyl (C7H7⋅) with phenyl (C6H5⋅) radicals in a pyrolytic reactor coupled with single photon ionization mass spectrometry. The unconventional mechanism of reaction is supported by theoretical calculations, which first produces diphenylmethane and unexpected 1‐(6‐methylenecyclohexa‐2,4‐dienyl)benzene intermediates (C13H12) accessed via addition of the phenyl radical to the ortho position of the benzyl radical. These findings offer convincing evidence for molecular mass growth processes defying conventional wisdom that radical‐radical reactions are initiated through recombination at their radical centers. The structure of 9H‐fluorene acts as a molecular building block for complex curved nanostructures like fullerenes and nanobowls providing fundamental insights into the hydrocarbon evolution in high temperature settings. [ABSTRACT FROM AUTHOR]

Ist Ladung wichtig? Direkte Vakuum ‐ UV ‐ Messungen von Ionisierungsenergien zeigen, dass die C ‐ H ‐ Insertion von Pt unter Bildung von H ‐ Pt ‐ CH3 hochexotherm ist, während die Bildung von PtCH2+H2 leicht endotherm ist. Experimente und Spin ‐ Bahn ‐ DFT ‐ Rechnungen zeigen überraschend ähnliche Energetiken für die Dehydrierung von Methan durch neutrales und kationisches Platin (rote Linien im Bild markieren experimentell bestimmte Energien). [ABSTRACT FROM AUTHOR]

The simplest polycyclic aromatic hydrocarbon (PAH) carrying a five‐membered ring—9H‐fluorene (C13H10)—is produced isomer‐specifically in the gas phase by reacting benzyl (C7H7⋅) with phenyl (C6H5⋅) radicals in a pyrolytic reactor coupled with single photon ionization mass spectrometry. The unconventional mechanism of reaction is supported by theoretical calculations, which first produces diphenylmethane and unexpected 1‐(6‐methylenecyclohexa‐2,4‐dienyl)benzene intermediates (C13H12) accessed via addition of the phenyl radical to the ortho position of the benzyl radical. These findings offer convincing evidence for molecular mass growth processes defying conventional wisdom that radical‐radical reactions are initiated through recombination at their radical centers. The structure of 9H‐fluorene acts as a molecular building block for complex curved nanostructures like fullerenes and nanobowls providing fundamental insights into the hydrocarbon evolution in high temperature settings. [ABSTRACT FROM AUTHOR]