An Unconventional Dark Radical Chemistry in Dense Molecular Clouds: Directed Gas-Phase Formation of Naphthyl Radicals #MMPMID41388989
Yang Z; Galimova GR; He C; Goettl SJ; Li X; Mebel AM; Kaiser RI
J Am Chem Soc 2025[Dec]; ? (?): ? PMID41388989show ga
The synthetic pathways to aromatic molecules inside photon-shielded dense molecular clouds remain a fundamental, unsolved enigma in astrochemistry and astrophysics, with low-temperature molecular growth routes involving aromatic radicals, such as prototype bicyclic naphthyl (C(10)H(7)(*)), implicated as key sources. Here, exploiting crossed molecular beam experiments augmented by electronic structure calculations, unexpected pathways are exposed leading to the gas-phase formation of 1- and 2-naphthyl via barrierless bimolecular reactions of atomic carbon (C) with indene (C(9)H(8)) and of dicarbon (C(2)) with styrene (C(8)H(8)) accompanied by ring expansion and cyclization together with aromatization. These facile routes challenge conventional wisdom that aromatic radicals are formed in deep space solely via "bright" gas-phase photochemistry of their closed-shell polycyclic aromatic hydrocarbon (PAH) precursors. A hitherto disregarded "dark" aromatic radical chemistry with aromatic radicals synthesized via gas-phase reactions offers new concepts on the chemical evolution of the chemistry of dark molecular clouds eventually culminating in the rapid formation of aromatics, fullerenes, and carbonaceous nanostructures.
J+Am+Chem+Soc 2025 ; ? (?): ?
