Metal-Free Organic Phosphors toward Fast and Efficient Room-Temperature Phosphorescence.

ConspectusMetal-free purely organic phosphors (POPs) are promising materials for display technologies, solid-state lighting, and sensors platforms because of their advantageous properties such as large design windows, easy processability, and economic material cost. Unlike inorganic semiconductors, creating the conditions for triplet excitons to produce light in organic materials is a demanding task because of the presence of electron spin configurations that undergo spin-forbidden transitions, which is usually facilitated by spin-orbit coupling (SOC). In the absence of heavy metals, however, the SOC efficiency in POPs remains low, and consequently, external nonradiative photophysical processes will also severely affect triplet excitons. Addressing these challenges requires the development of rational molecular design principles to accurately account for how all conceivable structural, electronic, chemical, compositional factors affect materials performance.This Account summarizes important molecular design and matrix engineering strategies to tackle the two key challenges for POPs─boosting SOC efficiencies and suppressing nonradiative decays. We start by reviewing the fundamental understanding of internal and external factors affecting the emission efficiencies of POPs, including the theory behind SOC and the origin of nonradiative decays. Subsequently, we discuss the design of contemporary POP systems on the basis of research insights from our group and others, where SOC is mostly promoted by heavy atom effects and the El-Sayed rule. On one hand, nonmetal heavy atoms including Br, I, or Se provide the heavy atom effects to boost SOC. On the other hand, the El-Sayed rule addresses the necessity of orbital angular momentum change in SOC and the general utilization of carbonyl, heterocyclic rings, and other moieties with rich nonbonding electrons. Because of the slow-decaying nature of triplet excitons, engineering the matrices of POPs is critical to effectively suppress collisional quenching as the major nonradiative decay route, thus achieving POPs with decent room temperature quantum efficiency. For that purpose, crystalline or rigid amorphous matrices have been implemented along with specific intermolecular forces between POPs and their environment.Despite the great efforts made in the past decade, the intrinsic SOC efficiencies of POPs remain low, and their emission lifetimes are pinned in the millisecond to second regime. While this is beneficial for POPs with ultralong emission, designing high-SOC POPs with simultaneous fast decay and high quantum efficiencies is particularly advantageous for display systems. Following the design of contemporary POPs, we will discuss molecular design descriptors that could potentially break the current limit to boost internal SOC in purely organic materials. Our recently developed concept of "heavy atom oriented orbital angular momentum manipulation" will be discussed, accompanied by a rich and expanded library of fast and efficient POP molecules, which serves as a stepping stone into the future of this field. We will conclude this Account by discussing the noteworthy application of POPs in organic light-emitting diodes (OLEDs), solid-state lighting, and sensors, as well as the remaining challenges in the design of fast and efficient POPs.