The synthesis of DMACBP, DMACPyBP, DMACBPN and DMACPyBPN is outlined in Scheme 1. To predict their optoelectronic properties, we first modelled the ground-state structure of the four emitters in the gas phase using density functional theory (DFT) at the PBE0/6-31G(d,p) level of theory (Figure ). The calculated energy levels of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) are shown in Figures and. As expected, the HOMO is localized on the DMAC donor while the LUMO is localized on the nitrogen-rich electron acceptors.