Here, a comprehensive photophysical investigation of a the emitter molecule DPTZ‐DBTO2, showing thermally activated delayed fluorescence (TADF), with near‐orthogonal electron donor (D) and acceptor (A) units is reported. It is shown that DPTZ‐DBTO2 has minimal singlet–triplet energy splitting due to its near‐rigid molecular geometry. However, the electronic coupling between the local triplet (³LE) and the charge transfer states, singlet and triplet, (¹CT, ³CT), and the effect of dynamic rocking of the D–A units about the orthogonal geometry are crucial for efficient TADF to be achieved. In solvents with low polarity, the guest emissive singlet ¹CT state couples directly to the near‐degenerate ³LE, efficiently harvesting the triplet states by a spin orbit coupling charge transfer mechanism (SOCT). However, in solvents with higher polarity the emissive CT state in DPTZ‐DBTO2 shifts below (the static) ³LE, leading to decreased TADF efficiencies. The relatively large energy difference between the ¹CT and ³LE states and the extremely low efficiency of the ¹CT to ³CT hyperfine coupling is responsible for the reduction in TADF efficiency. Both the electronic coupling between ¹CT and ³LE, and the (dynamic) orientation of the D–A units are thus critical elements that dictate reverse intersystem crossing processes and thus high efficiency in TADF.

A series of phenothiazine–dibenzothiophene-S,S-dioxide charge-transfer molecules have been synthesized. Increasing steric restriction around the donor–acceptor bond significantly alters contributions from TADF and phosphorescence. Bulky substituents on the 1-(and 9) position(s) of the phenothiazine result in no TADF in the solid state; instead strong phosphorescence is observed at ambient temperature.

The synthesis of 1-methylphenoxazine via CO2-directed lithiation chemistry is reported. This electron donor was coupled with 2,8-dibenzothiophene-S,S-dioxide with Buchwald–Hartwig chemistry to give a new D–A–D charge-transfer fluorescent molecule 1b. X-ray crystal structures and calculations show that the phenoxazinyl groups are coplanar and equatorial (eq) to the acceptor plane in non-methylated 1a, but are pyramidal and axial (ax) in 1b. The bond rotation energy barriers between donor and acceptor groups for 1a and 1b are only 0.13 and 0.19 eV respectively from hybrid-DFT computations at the CAM-B3LYP/6-31G(d) level. Many possible conformers are present in solutions and in zeonex. In zeonex, the methyl groups in 1b shift the emission band 0.13 eV higher in energy compared to 1a. Excited state eq-eq and ax-ax geometries were identified with DFT calculations, with charge transfer (CT) emission assigned as 1CT(eq) and 1CT(ax) dominating. The lower energy 1CT(eq) contributes to thermally activated delayed fluorescence (TADF), whereas the higher energy 1CT(ax) does not. Phenothiazine analogs 2a and 2b, also have major fluorescence emissions assigned as 1CT(eq) and 1CT(ax) respectively. 2a-b have substantial room temperature phosphorescence (RTP) whereas 1a-b do not, highlighting the importance of the sulfur atom in 2a-b to obtain RTP emission.