The formation of the simplest polycyclic aromatic hydrocarbon (PAH), naphthalene (CH), was explored in a high-temperature chemical reactor under combustion-like conditions in the phenyl (CH)-vinylacetylene (CH) system. The products were probed utilizing tunable vacuum ultraviolet light by scanning the photoionization efficiency (PIE) curve at a mass-to-charge m/ z = 128 (CH) of molecules entrained in a molecular beam. The data fitting with PIE reference curves of naphthalene, 4-phenylvinylacetylene (CHCCCH), and trans-1-phenylvinylacetylene (CHCHCHCCH) indicates that the isomers were generated with branching ratios of 43.5±9.0 : 6.5±1.0 : 50.0±10.0%. Kinetics simulations agree nicely with the experimental findings with naphthalene synthesized via the hydrogen abstraction-vinylacetylene addition (HAVA) pathway and through hydrogen-assisted isomerization of phenylvinylacetylenes. The HAVA route to naphthalene at elevated temperatures represents an alternative pathway to the hydrogen abstraction-acetylene addition (HACA) forming naphthalene in flames and circumstellar envelopes, whereas in cold molecular clouds, HAVA synthesizes naphthalene via a barrierless bimolecular route.

The hydrogen-abstraction/acetylene-addition (HACA) mechanism has been central for the last decades in attempting to rationalize the formation of polycyclic aromatic hydrocarbons (PAHs) as detected in carbonaceous meteorites such as in Murchison. Nevertheless, the basic reaction mechanisms leading to the formation of even the simplest tricyclic PAHs like anthracene and phenanthrene are still elusive. Here, by exploring the previously unknown chemistry of the ortho-biphenylyl radical with acetylene, we deliver compelling evidence on the efficient synthesis of phenanthrene in carbon-rich circumstellar environments. However, the lack of formation of the anthracene isomer implies that HACA alone cannot be responsible for the formation of PAHs in extreme environments. Considering the overall picture, alternative pathways such as vinylacetylene-mediated reactions are required to play a crucial role in the synthesis of complex PAHs in circumstellar envelopes of dying carbon-rich stars.

Polycyclic aromatic hydrocarbons (PAHs) have been invoked in fundamental molecular mass growth processes in our galaxy. We provide compelling evidence of the formation of the very first ringed aromatic and building block of PAHs—benzene—via the self-recombination of two resonantly stabilized propargyl (C3H3) radicals in dilute environments using isomer-selective synchrotron-based mass spectrometry coupled to theoretical calculations. Along with benzene, three other structural isomers (1,5-hexadiyne, fulvene, and 2-ethynyl-1,3-butadiene) and o-benzyne are detected, and their branching ratios are quantified experimentally and verified with the aid of computational fluid dynamics and kinetic simulations. These results uncover molecular growth pathways not only in interstellar, circumstellar, and solar systems environments but also in combustion systems, which help us gain a better understanding of the hydrocarbon chemistry of our universe.

A synthetic route to racemic helicenes via a vinylacetylene mediated gas phase chemistry involving elementary reactions with aryl radicals is presented. In contrast to traditional synthetic routes involving solution chemistry and ionic reaction intermediates, the gas phase synthesis involves a targeted ring annulation involving free radical intermediates. Exploiting the simplest helicene as a benchmark, we show that the gas phase reaction of the 4-phenanthrenyl radical ([C 14 H 9 ] • ) with vinylacetylene (C 4 H 4 ) yields [4]-helicene (C 18 H 12 ) along with atomic hydrogen via a low-barrier mechanism through a resonance-stabilized free radical intermediate (C 18 H 13 ). This pathway may represent a versatile mechanism to build up even more complex polycyclic aromatic hydrocarbons such as [5]- and [6]-helicene via stepwise ring annulation through bimolecular gas phase reactions in circumstellar envelopes of carbon-rich stars, whereas secondary reactions involving hydrogen atom assisted isomerization of thermodynamically less stable isomers of [4]-helicene might be important in combustion flames as well.