For the first time the kinetic rate constants of the UV photolysis of polyynes C6H2, C8H2, C10H2, C12H2 and C14H2 under rigorously inert atmosphere have been determined in three different solvents: n-hexane, n-heptane and decalin. First- or pseudofirst-order kinetics appear suitable to describe the photolysis of these molecules and k values in the range between 3.0×10−3 s−1 and 4.6×10−3 s−1 have been determined. The unique exception is represented by C6H2 which photolyses more slowly with k=3.2×10−4 s−1. Two different UV sources have been used in the present study: a low-pressure mercury lamp having a monochromatic emission at 253.7 nm and a medium-to high-pressure lamp with a continuous emission between 222 nm and 580 nm. The results are of interest in the understanding, and also the modelling, of the fate of polyynes released by carbon-rich stars in the interstellar medium or the polyynes released by comets in their active phase.

Monocyanopolyynes are formed by arcing graphite electrodes in ammonia. This work completes the parallelism existing between the polyynes formed by laser ablation experiments of graphite targets and those produced from the submerged electric arc. In both cases the same products are obtained. The products consist of hydrogen-terminated polyynes if water is present, monocyanopolyynes (mixed with hydrogen-terminated polyynes) if the carbon arc is sparked in acetonitrile or ammonia and dicyanopolyynes if the arc is struck in liquid nitrogen. The mechanism of formation of polyynes in the submerged carbon arc involves essentially neutral species; similar species and pathways may also occur in the circumstellar environment where polyynes have been detected by radioastronomy. It is shown that the relative abundances of the polyynes formed in the submerged carbon arc or in a carbon arc in vacuum decrease by a factor between three and five as the chain length increases by a C2 unit. Exactly the same trend has been observed by radioastronomy both for polyynes and cyanopolyynes in the circumstellar environment around red giants and asymptotic giant branch (AGB) stars. This fact may be a simple coincidence or may suggest that the mechanism of formation of the polyynes in the carbon arc is the same as that occurring in the surroundings of carbon-rich stars.

Monocyanopolyynes and dicyanopolyynes can be synthesized quite easily by the submerged electric arc. Monocyanopolyynes having the general formula H[bond](C[triple bond]C)n[bond]C[triple bond]N can be synthesized together with ordinary polyynes series H[bond](C[triple bond]C)n[bond]H by arcing graphite electrodes in acetonitrile. Dicyanopolyynes N[triple bond]C[bond](C[triple bond]C)n[bond]C[triple bond]N are produced almost pure by arcing graphite electrodes directly into liquid nitrogen. These molecules are present in the envelope of post-AGB (asymptotic giant branch), carbon-rich giant stars and also in dark molecular clouds. They are incorporated into comets and also into other primitive materials and may play a role in the prebiotic synthesis of more complex organic molecules having a biological significance. Furthermore, the cyanopolyynes are involved in the atmospheric chemistry of some bodies of the solar system. The discovery of the easy formation of these molecules under laboratory conditions may explain why these molecules are so ubiquitous in space and may also stimulate new ideas about the mechanism of their formation.

Crossed-beam experiments on the reactions of cyano CN(X2Σ+) and ethinyl C2H(X2Σ+) radicals with the unsaturated hydrocarbons acetylene, ethylene, methylacetylene allene and benzene have been carried out under single-collision conditions to investigate synthetic routes to form nitriles, polyynes and substituted allenes in hydrocarbon-rich atmospheres of planets and their moons. All reactions were found to proceed without an entrance barrier, to have exit barriers well below the energy of the reactant molecules and to be strongly exothermic. The predominant identification of the radical versus atomic hydrogen exchange channel makes these reactions compelling candidates for the formation of complex organic chemicals – precursors to biologically important amino acids – in Solar system environments and in the interstellar medium.