Design of Anti-Hund Organic Emitters Based on Heptazine.

Abstract

Hund's rule, which is powerful in governing the first excited states of closed-shell organic materials, can hardly be violated to get inverted singlet-triplet gap (INVEST) molecules with negative singlet-triplet energy gaps (ΔEST), although INVEST materials have shown extraordinary photophysical properties and promising device performance especially in light-emitting diodes. Here, we propose a facile strategy to construct emissive INVEST molecules by introducing different types of substituents to heptazine in various modes, which can effectively tune the ΔEST to be negative with the enlarged oscillator strength (f) for the high fluorescence rate of the heptazine derivatives. Systematic computational studies show that the double substitution of electron-donating units with another nonconjugated substituent in hybrid substitution mode is the most favorable way in achieving slightly negative ΔEST and large f values; the conjugated substituent will compete with heptazine to make the molecule deviate from the INVEST feature. Especially, a series of high-performance heptazine-based INVEST emitters were constructed, exhibiting ΔEST low to -0.362 eV, f up to 0.0436, as well as a wide range emission color from 339 to 716 nm. Also, the designed molecules were predicted to have fluorescence radiative rates up to 106 s-1, along with efficient reverse intersystem crossing rates reaching 108 s-1. Importantly, the figure of merit (FM) was first proposed as a parameter to wholly evaluate the performance of INVEST emitters, and the highest FM of 0.198 was found in the triazine and double nonconjugated amine-substituted heptazine. These results highlight the great potential of the heptazine chromophore in constructing INVEST emitters, revealing fundamental structure-property understandings for the material design of efficient anti-Hund organic molecules with improved emission properties.