Push-pull hyperbranched molecules. A theoretical study

摘要

The electronic properties of the ground state, unrelaxed and relaxed first excited states of push-pull hyperbranched molecules bearing amino and nitro terminal groups have been studied at B81K/cc-pvdz//HF/6-31g(d), TD-BB1K/cc-pvdz//HF/6-31g(d) and TD-BB1K/cc-pvdz//CIS/6-31g(d) levels of theory, respectively. It was demonstrated that dendritic architecture of push-pull molecules favours the charge transfer in the excited state compared to linear molecules. The possibility of adopting a plane conformation is an important condition for the charge transfer in an excited state. According to the calculations 1:1 ratio of donor and acceptor groups is another important precondition for the manifestation of strong charge separation in the excited state. In case of excess of nitro groups over the amino, some of the excitations participating in the S0 -> S1 transition favour the charge transfer in the excited state in the opposite directions, thus decreasing the charge separation. Copyright (c) 2008 John Wiley & Sons, Ltd.