Isotope scrambling in the formation of cyanopolyynes by laser ablation of carbon particles in liquid acetonitrile

Cyanopolyynes, H(CC)_nCN (n = 3–6), were formed by laser ablation of carbon particles in liquid acetonitrile. The molecules were separated according to the size n and characterized by UV absorption spectroscopy, mass spectroscopy in combination with gas-chromatographic separation, and nuclear magnetic resonance (NMR) spectroscopy. For the study of nascent carbon cluster distribution during the growth of the long carbon chain molecules, isotopomer distribution was analyzed by NMR spectroscopy for the product molecules. Two cyanopolyynes of HC₇N and HC₉N were isolated from solutions after laser ablation of isotope-enriched carbon powder (99% ¹³C) in liquid acetonitrile, CH₃CN, of natural isotopic abundance (1.1% ¹³C). With the observed chemical shift, δ, and spin–spin coupling constants, J_CH and J_CC, spectral simulation was made to determine relative abundance of possible isotopomeric forms for HC₉N. We found that the isotope of ¹²C, mostly from solvent molecules, contributes substantially for the part of carbon in the cyano group, –CN, in HC₉N. The isotopomer distribution observed for the sequence of H–CC–CC– was fairly explainable by a binomial, random distribution of the two carbon isotopes of ¹²C and ¹³C, reducing the concentration of ¹³C to 76–55%.