Multireference configuration interaction methods including spin-orbit interactions have been employed to investigate the photophysical properties of various linear N-heterocyclic carbene (NHC) copper(I) pyridine complexes with the aim of designing performant thermally activated delayed fluorescence (TADF) emitters for use in organic-light-emitting diodes. Our theoretical results indicate that this structural motif is very favorable for generating excited triplet states with high quantum yield. The first excited singlet (S-MLCT) and corresponding triplet state (T-MLCT) are characterized by d(sigma) -> pi(Py) metal-toligand charge-transfer (MLCT) excitations. Efficient intersystem crossing (ISC) and reverse ISC (rISC) between these states is mediated by a near-degenerate second triplet state (TMLCT/LC) with large d(pi) -> pi(Py) contributions. Spin-vibronic coupling is strong and is expected to play a major role in the (r)ISC processes. The calculations reveal, however, that the luminescence is effectively quenched by locally excited triplet states if the NHC ligand carries two diisopropylphenyl (DIPP) substituents. When DIPP is replaced with 1-adamantyl residues, this quenching process is suppressed and TADF in the UV spectral regime is predicted to proceed at a rate of about 1/mu s. The introduction of +I substituents on the carbene and -M substituents on the pyridine allows tuning of the emission wavelength from the UV to the blue-green or green spectral region.