The conformational dependence of the matrix element for spin–orbit coupling and of the electronic coupling for charge separation are determined for an electron donor–acceptor system containing a pyrene acceptor and a dimethylaniline donor. Different kinetic and energetic aspects that play a role in the spin–orbit charge transfer intersystem crossing (SOCT-ISC) mechanism are discussed. This includes parameters related to initial charge separation and the charge recombination pathways using the Classical Marcus Theory of electron transfer. The spin–orbit coupling, which plays a significant role in charge recombination to the triplet state, can be probed by (TD)-DFT, using the latter as a tool to understand and predict the SOCT-ISC mechanism. The matrix elements for spin–orbit coupling for acetone and 4-thio-thymine are used for benchmarking. (Time Dependent-) Density Functional Theory (DFT and TD-DFT) calculations are applied using the quantum chemical program Amsterdam Density Functional (ADF).

In order to investigate the joint influence of the conformation flexibility and the matching of the energies of the charge-transfer (CT) and the localized triplet excited (³LE) states on the thermally activated delayed fluorescence (TADF) in electron donor–acceptor molecules, a series of compact electron donor–acceptor dyads and a triad were prepared, with naphthalimide (NI) as electron acceptor and phenothiazine (PTZ) as electron donor. The NI and PTZ moieties are either directly connected at the 3-position of NI and the N-position of the PTZ moiety via a C–N single bond, or they are linked through a phenyl group. The tuning of the energy order of the CT and LE states is achieved by oxidation of the PTZ unit into the corresponding sulfoxide, whereas conformation restriction is imposed by introducing ortho-methyl substituents on the phenyl linker, so that the coupling magnitude between the CT and the ³LE states can be controlled. The singlet oxygen quantum yield (Φ_Δ) of NI-PTZ is moderate in n-hexane (HEX, Φ_Δ = 19%). TADF was observed for the dyads, the biexponential luminescence lifetime are 16.0 ns (99.9%)/14.4 μs (0.1%) for the dyad and 7.2 ns (99.6%)/2.0 μs (0.4%) for the triad. Triplet state was observed in the nanosecond transient absorption spectra with lifetimes in the 4–48 μs range. Computational investigations show that the orthogonal electron donor–acceptor molecular structure is beneficial for TADF. These calculations indicate small energetic difference between the ³LE and ³CT states, which are helpful for interpreting the ns-TA spectra and the origins of TADF in NI-PTZ, which is ultimately due to the small energetic difference between the ³LE and ³CT states. Conversely, NI-PTZ-O, which has a higher CT state and bears a much more stabilized ³LE state, does not show TADF.

In order to investigate the joint influence of the conformation flexibility and the matching of the energies of the charge-transfer (CT) and the localized triplet excited (³LE) states on the thermally-activated delayed fluorescence (TADF) in electron donor-acceptor molecules, a series of compact electron donor-acceptor dyads and triad were prepared, with naphthalimide (NI) as electron acceptor and phenothiazine (PTZ) as electron donor. The NI and PTZ moieties are either directly connected at 3-position of NI and N-position of PTZ moiety via a C-N single bond, or are linked through a phenyl group. The tuning of the energy order of the CT and LE states is achieved by oxidation of the PTZ unit into the corresponding sulfoxide, whereas conformation restriction is imposed by introducing ortho-methyl substituents on the phenyl linker, thus the coupling magnitude between the CT and the ³LE states are controlled. Singlet oxygen quantum yields (F_D) of NI-PTZ is moderate in n-hexane (HEX, Φ_Δ = 19%). TADF was observed for the dyads, the biexponential luminescence lifetime are 16.0 ns (99.9%)/14.4 μs (0.1%) for the dyad and 7.2 ns (99.6%)/2.0 μs (0.4%) for the triad. The triplet state was observed in the nanosecond transient absorption spectra with lifetimes: in the 4-48 μs range. Computational investigations show that the orthogonal electron donor-acceptor molecular structure is beneficial for TADF. These calculations also help interpreting the ns-TA spectra and the origins of TADF in NI-PTZ, which is ultimately due to the small energetic difference between the ³LE and ³CT states. Conversely, NI-PTZ-O, which has a higher CT state and bear a much more stabilized ³LE state, does not display TADF.

The conformational dependence of the matrix element for spin-orbit coupling and of the electronic coupling for charge separation are determined for an electron donor-acceptor system containing a pyrene acceptor and a dimethylaniline donor. Different kinetic and energetic aspects that play a role in the spin-orbit charge transfer intersystem crossing (SOCT-ISC) mechanism are discussed. This includes parameters related to initial charge separation and the charge recombination pathways using the (Semi-Classical) Marcus Theory for electron transfer. The spin-orbit coupling, which plays a significant role in charge recombination to the triplet state can be probed by (TD-)DFT, using the latter as a tool to understand and predict the SOCT-ISC mechanism. The matrix elements for spin-orbit coupling for acetone and 4-thio-thymine are used for benchmarking. (Time Dependent-) Density Functional Theory (DFT and TD-DFT) calculations are applied using the quantum chemical program Amsterdam Density Functional (ADF).