Modern emitter design is frequently aided by in silico modelling. Density functional theory (DFT) can predict the energies of both singlet and triplet excited states via the time-dependent (TD-)DFT formalism. These calculations are able to predict real-world trends among a series of compounds. Accurate prediction of absolute energies is also possible, but is more challenging to achieve since it requires the proper inclusion of multiple effects such as solvent stabilization, changes in the excited-state geometry, vibronic effects, as well as conformational disorder. In addition to energies, TD-DFT can also calculate the oscillator strength and the nature of the excited sate. The oscillator strength closely relates to the radiative decay rate and thus the ΦPL, and larger values correspond to a more probable transition. Meanwhile, the 'nature' of the excited state indicates which molecular orbitals contribute to the transition, and from the localization of these orbitals around the molecule it is possible to estimate the degree of charge-transfer (CT) or locally-excited (LE) character of the excited state, and which molecular units of the molecule are involved in the electronic transition. DFT can also calculate the energies of the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO respectively), which can be used to quantify the strength of the donor and acceptor moieties of the emitter. A more stabilised LUMO and more destabilised HOMO correspond to a stronger acceptor and stronger donor, respectively. Finally, it is also possible to calculate the spin-orbit coupling (SOC, HSO) between two excited states of different spin multiplicities, which in the case of TADF involves a singlet and a triplet excited state. This property indicates the degree of coupling between the two states which thus opens both intersystem and reverse-intersystem crossing pathways, both of prime importance when discussing the TADF mechanism. TADF emitter design typically targets minimising ΔEST by localising the hole and the electron densities (for a two-state electronic transition, these usually correspond to the HOMO and LUMO, respectively) of the emitter to a (number of) donor and acceptor moieties. These moieties are then typically linked via an aromatic bridge 7 to ensure sufficient overlap between the HOMO and LUMO, which is necessary to maintain a large oscillator strength and thus efficient fluorescence. The most commonly used aromatic bridge is benzene, yet its larger homolog, naphthalene, has been used only rarely. This is curious, both because naphthalene is bulkier than benzene and ought to induce larger torsion angles between the donor/acceptor and the central bridge, which is beneficial for reducing ΔEST, and also because the larger π-system possesses a more stabilised LUMO, opening the possibility of using naphthalene itself as the electron-accepting moiety. Indeed, of the plethora of OLED emitters, only three notable reports can be found of compounds containing naphthalene (Figure ). These are: (1) 1,4-naphthyl-CF3 and 1,5-Naphthyl-CF3, two fluorescent blue (λEL = 453 and 446 nm, respectively) donor-bridge-acceptor emitters where naphthalene acts as a bridge 9 that show moderate FPL (67 and 36%, respectively) in toluene solution.