A "Flexible" Purely Organic Molecule Exhibiting Strong Spin-Orbital Coupling: Toward Nondoped Room-Temperature Phosphorescence OLEDs

J Phys Chem Lett. 2022 Jun 9;13(22):4971-4980. doi: 10.1021/acs.jpclett.2c01205. Epub 2022 May 31.

Abstract

Purely organic materials usually exhibit weak spin-orbital coupling (SOC) effect because of the lack of noble heavy metals, and the generation and direct emission from the triplet state is spin-forbidden. This would lead to slow intersystem crossing, long triplet lifetime, and low phosphorescence quantum yield. Herein, strong spin-orbital coupling between singlet and triplet was observed in a "flexible" and twist thianthrene-pyrimidine-based purely organic compound in an amorphous film state, which shows a fast intersystem crossing process and a high phosphorescence rate of 1.1 × 103 s-1. The heavy atom sulfur and nitrogen atoms in the molecule can provide n-π* transition character for efficient spin-orbital coupling. Moreover, the flexible molecule skeleton enables conformational change and molecular vibration in excited states, which was proved to be vital for efficient vibrational spin-orbital coupling. Benefitting from the strong SOC effect, a nondoped purely organic phosphorescence light-emitting diode was fabricated, which achieves a maximum external quantum efficiency of 7.98%, corresponding to an exciton utilization ratio exceeding 87.6%.