| Abstract: | Quantum mechanics calculations at B3LYP/6‐31G (d)//HF/3‐21G (d) level of the theory were carried out on second generation dendritic polyacetylenic oligomers bearing different terminal groups to clarify the impact of their nature on the electronic structure of hyperbranched polyacetylene. It was found that steric and electronic factors affect the electronic properties of the studied dendrimers. While the steric hindrances independently of the nature of a terminal group tend to increase band gap and ionisation potential and decrease electron affinity, the interaction of lone electron pairs and π‐electrons of the terminal groups with the rest of the molecule produces specific changes in the electronic structure of each particular group. A general feature of the studied dendrimers is that upon ionisation or addition of an electron to the dendrimer the molecules become more planar. |
