Computational characterization of carbazole-benzonitrile derivatives for applications in Organic Light Emitting Diodes

The technology of Organic Light-Emitting Diodes has reached such a high level of reliability that it can be used in various applications. The required light emission efficiency can be achieved by transforming the triplet excitons into singlet states through Reverse InterSystem Crossing (RISC), which is the main process of a general mechanism called thermally activated delayed fluorescence (TADF). In this thesis, we theoretically analyzed two carbazole-benzonitrile (donor-acceptor) derivatives, 2,5-di(9H-carbazol-9-yl)benzonitrile (p-2CzBN) and 2,3,4,5,6-penta(9H-carbazol-9-yl)benzonitrile (5CzBN), and addressed the problem of how donor-acceptor (D-A) or donor-acceptor-donor (D-A-D) flexible molecular architectures influence the nature of the excited states and the emission intensity. Furthermore, we analyzed the RISC rates as a function of the conformation of the carbazole lateral groups, considering the first electronic states, S0, S1, T1 and T2, involved in TADF process. The two prototype molecules, p-2CzBN and 5CzBN, have a similar energy gap between the first singlet and triplet states (∆EST, a key parameter in the RISC rate), but different TADF performances. Therefore, other parameters must be considered to explain their different behavior. The oscillator strength of p-2CzBN, never tested as emitter in OLEDs, is similar to that of 5CzBN, which is an active TADF molecule. We also note that the presence of a second T2 triplet state, lower in energy than S1 only in 5CzBN, and the reorganization energies, associated with RISC processes involving T1 and T2, are important factors in differentiating the rates in p-2CzBN and 5CzBN. For p-2CzBN, the RISC rate from T2 to S1 is surprisingly higher than that from T1 to S1, in disagreement with El-Sayed rules, due to a large reorganization energy associated to the T1 to S1, process; while the contrary occurs for 5CzBN. These insights are important for designing new TADF emitters based on the benzo-carbazole architecture