RESUMO
We expose significant changes in the emission color of carbazole-based thermally activated delayed fluorescence (TADF) emitters that arise from the presence of persistent dimer states in thin films and organic light-emitting diodes (OLEDs). Direct photoexcitation of this dimer state in 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) reveals the significant influence of dimer species on the color purity of its photoluminescence and electroluminescence. The dimer species is sensitive to the sample preparation method, and its enduring presence contributes to the widely reported concentration-mediated red shift in the photoluminescence and electroluminescence of evaporated thin films. This discovery has implications on the usability of these, and similar, molecules for OLEDs and explains disparate electroluminescence spectra presented in the literature for these compounds. The dimerization-controlled changes observed in the TADF process and photoluminescence efficiency mean that careful consideration of dimer states is imperative in the design of future TADF emitters and the interpretation of previously reported studies of carbazole-based TADF materials.
RESUMO
Regio- and conformational isomerization are fundamental in chemistry, with profound effects upon physical properties, however their role in excited state properties is less developed. Here two regioisomers of bis(10H-phenothiazin-10-yl)dibenzo[b,d]thiophene-S,S-dioxide, a donor-acceptor-donor (D-A-D) thermally-activated delayed fluorescence (TADF) emitter, are studied. 2,8-bis(10H-phenothiazin-10-yl)dibenzo[b,d]thiophene-S,S-dioxide exhibits only one quasi-equatorial conformer on both donor sites, with charge-transfer (CT) emission close to the local triplet state leading to efficient TADF via spin-vibronic coupling. However, 3,7-bis(10H-phenothiazin-10-yl)dibenzo[b,d]thiophene-S,S-dioxide displays both a quasi-equatorial CT state and a higher-energy quasi-axial CT state. No TADF is observed in the quasi-axial CT emission. These two CT states link directly to the two folded conformers of phenothiazine. The presence of the low-lying local triplet state of the axial conformer also means that this quasi-axial CT is an effective loss pathway both photophysically and in devices. Importantly, donors or acceptors with more than one conformer have negative repercussions for TADF in organic light-emitting diodes.
RESUMO
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.
