Molecular modelling of hyperbranched polyacetylene

Ab initio and density functional theory calculations carried out on linear and dendritic polyacetylenic (PA) oligomers of different size showed that acetylenic dendrimers are less stable than trans‐PA oligomers and that the instability increases with molecular weight reflecting the strain in crowded hyperbranched structures. However, the energy difference between linear and dendritic structure is rather small and tends to a limit with molecular weight. Twisting of the double bonds decreases the conjugation in hyperbranched PA compared to linear trans‐PA. However, the conjugation though less effective than in trans‐PA is extended up to the 4^th or 5^th generation of dendrimers. It was shown that bromine end groups strongly affect the electronic properties of acetylenic dendrimers decreasing even more the conjugation due to the sterical hindrances, however, highly polarizable bromine atoms reduced significantly the adiabatic potentials of ionization to be very close to that for trans‐PA oligomers.