Constructing high-performance TADF polymers from non-TADF monomers: a computational investigation

Thermally activated delayed fluorescence (TADF) polymers excelling in simple, low-cost and large-area solution process ability have attracted tremendous attention recently, but it remains a great challenge for the design of such materials due to the lack of reliable molecular construction guidelines. Here we perform a systematic computational investigation on the construction of TADF polymers from non-TADF monomers to elucidate the effects of polymerization sites, substituent positions and substituent types. The results indicate that the polymerization of 3,6-carbazole-based monomers with different substituents is efficient to build TADF polymers due to their facile pi-conjugation extendability. Especially, polymers with para-phenyl-substituted monomers are promising in light of their separated frontier molecular orbitals for small Delta E-ST with favorable energy levels, bipolar charge transport properties and relatively strong absorption/emission intensity, which should be highly attractive for experimental investigations. These findings and insights are important in revealing the structure-property relation of TADF polymers made from non-TADF monomers with important clues for understanding the construction mechanism and molecular design principles of TADF polymers.