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Roaming dynamics have been shown to be important in unimolecular decompositions, but the relevance to bimolecular reactions has been less clear. Here, the authors study radical addition/elimination reactions and implicate a roaming transition state in a bimolecular reaction.

The rapid dissociation of methanetetrol has been suggested as an impediment to its observation, despite the stability of its substituted derivative orthocarbonates. The authors identify methanetetrol as a product of carbon dioxide and water reactions in space-simulation experiments via photoionization mass spectrometry working in tandem with computation quantum chemistry.

Helicenes represent key building blocks leading eventually to carbonaceous nanostructures. Here, exploiting [4]-helicene as a benchmark, the authors present a synthetic route to racemic helicenes via a vinylacetylene mediated gas phase chemistry with aryl radicals involving ring annulation.

Polycyclic aromatic hydrocarbons (PAHs) represent key molecular building blocks in extraterrestrial environments but the understanding of their formation and growth in this environment has remained elusive. Here the authors reveal how naphthalene can be efficiently formed via rapid radical–radical reactions.

A pathway towards the formation of pyridine and (iso)quinoline, precursors to DNA and RNA, is revealed for conditions appropriate to Saturn’s moon Titan and the Taurus molecular cloud, providing insight into the synthesis of prebiotic molecules in space.

Nanobowls represent building blocks of fullerenes and nanotubes as detected in combustion systems and deep space, but their formation mechanisms in these environments have remained elusive. Here, the authors explore the gas-phase formation of benzocorannulene and beyond to the C₄₀ nanobowl.

The reaction of benzyl radical self-reaction to anthracene opens-up a previously overlooked avenue for a more efficient synthesis of aromatic, multi-ringed structures via excited state dynamics in the gas phase.

Small polycyclic aromatic hydrocarbons (PAHs) are thought to be nucleation sites for the growth of Titan’s haze layers. Using laboratory experiments and electronic structure calculations, Zhao et al. show that small PAHs can by synthesized by rapid, barrierless reactions in Titan’s low-temperature environments.

Pyrene, a polycyclic aromatic hydrocarbon composed of four fused benzene rings, is putatively a key molecule in the formation of 2D carbonaceous structures. Using experimental and computational techniques, Zhao et al. show that pyrene can form in circumstellar conditions.

Interstellar silicates play a key role in star formation, however their synthetic routes are not fully understood. Here, the authors provide evidence for the formation of SiO₂ along with SiO via low-temperature gas phase chemistry.