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Materials exhibiting thermally activated delayed fluorescence (TADF) have been extensively explored in the last decade. These emitters have great potential of being used in organic light-emitting diodes because they allow for high quantum efficiencies by utilizing triplet states via reverse intersystem crossing. In small molecules, this is done by spatially separating the highest occupied molecular orbital from the lowest unoccupied molecular orbital, forming an intramolecular charge-transfer (iCT) state and leading to a small energy difference between lowest excited singlet and triplet states (Δ E ST ). However, in polymer emitters, this is harder to achieve, and typical strategies usually include adding known TADF units as sidechains onto a polymer backbone. In a previous work, we proposed an alternative way to achieve a TADF polymer by repeating a non-TADF unit, polymerizing it via electron-donating carbazole moieties. The extended conjugation on the backbone reduced the Δ E ST and allowed for an efficient TADF polymer. In this work, we present a more in-depth study of the shift from a non-TADF monomer to TADF oligomers. The monomer shows non-TADF emission, and we find the delayed emission to be of triplet-triplet annihilation origin. An iCT state is formed already in the dimer, leading to a much more efficient TADF emission. This is confirmed by an almost two-fold increase of photoluminescence quantum yield, a decrease in the delayed luminescence lifetime, and the respective spectral lineshapes of the molecules.

Amorphous purely organic thin films are able to show efficient phosphorescence under ambient conditions at room temperature. This opens the perspective to a wide range of new applications, which have attracted lots of interest in the field of material science recently. Therefore, an increasing number of different molecules displaying room temperature phosphorescence (RTP) have already been reported. Whereas the efficiency, the lifetime, or the oxygen sensitivity is frequently discussed, the origin of RTP mainly remains vague. Often, material design rules tend to the development of increasingly complex structures. Here, the well-known tetra- N -phenylbenzidine (TPD), an archetypical material showing highly efficient fluorescence and RTP, is broken down to its fragments. As the complexity of the system decreases with the molecule's size, spectroscopic investigation of this molecular family enables a deeper understanding of the appearance of RTP. With spectral and time-resolved measurements, RTP can be detected for all compounds containing a biphenyl core, with lifetimes up to 0.9 s under inert gas conditions. These findings form the basis of a deeper understanding of the appearance of RTP in organic molecules and therefore allow for a more focused investigation of new materials.