The study of purely organic room-temperature phosphorescence (RTP) has drawn increasing attention because of its considerable theoretical research and practical application value. Currently, organic RTP materials with both high efficiency (ΦP  > 20%) and a long lifetime (τP  > 10 s) in air are still scarce due to the lack of related design guidance. Here, a new strategy to increase the phosphorescence performance of organic materials by integrating the RTP host and RTP guest in one doping system to form a triplet exciplex, is reported. With these materials, the high-contrast labeling of tumors in living mice and encrypted patterns in thermal printing are both successfully realized by taking advantage of both the long afterglow time (up to 25 min in aqueous media) and high phosphorescence efficiency (43%).

High Performance of Simple Organic Phosphorescence Host-Guest Materials and their Application in Time-Resolved Bioimaging.

Nonconventional luminophores devoid of remarkable conjugates have attracted considerable attention due to their unique luminescence behaviors, updated luminescence mechanism of organics and promising applications in optoelectronic, biological and medical fields. Unlike classic luminogens consisting of molecular segments with greatly extended electron delocalization, these unorthodox luminophores generally possess nonconjugated structures based on subgroups such as ether (–O–), hydroxyl (–OH), halogens, carbonyl (CO), carboxyl (–COOH), cyano (CN), thioether (–S–), sulfoxide (SO), sulfone (OSO), phosphate, and aliphatic amine, as well as their grouped functionalities like amide, imide, anhydride and ureido. They can exhibit intriguing intrinsic luminescence, generally featuring concentration-enhanced emission, aggregation-induced emission, excitation-dependent luminescence and prevailing phosphorescence. Herein, we review the recent progress in exploring these nonconventional luminophores and discuss the current challenges and future perspectives. Notably, different mechanisms are reviewed and the clustering-triggered emission (CTE) mechanism is highlighted, which emphasizes the clustering of the above mentioned electron rich moieties and consequent electron delocalization along with conformation rigidification. The CTE mechanism seems widely applicable for diversified natural, synthetic and supramolecular systems.

Nonconventional luminophores: characteristics, advancements and perspectives.

Organic room temperature phosphorescence (RTP) materials have been used in high resolution imaging and anticounterfeiting due to their long lifetime of phosphorescence ability to avoid interference...

Recent Progress in Pure Organic Room Temperature Phosphorescence of Small Molecular Host–Guest Systems

Stimulus-Responsive Room Temperature Phosphorescence Materials: Internal Mechanism, Design Strategy, and Potential Application

ConspectusLong-lived organic room-temperature phosphorescence (RTP) materials have recently drawn extensive attention because of their promising applications in information security, biological imaging, optoelectronic devices, and intelligent sensors. In contrast to conventional fluorescence, the RTP phenomenon originates from the slow radiative transition of triplet excitons. Thus, enhancing the intersystem crossing (ISC) rate from the lowest excited singlet state (S1) to the excited triplet state and suppressing the nonradiative relaxation channels of the lowest excited triplet state (T1) are reasonable methods for realizing highly efficient RTP in purely organic materials. Over the past few decades, many strategies have been designed on the basis of the above two crucial factors. The introduction of heavy atoms, aromatic carbonyl groups, and other heteroatoms with abundant lone-pair electrons has been demonstrated to strengthen the spin-orbit coupling, thereby successfully facilitating the ISC process. Furthermore, the rigid environment is commonly constructed through crystal engineering to restrict intramolecular motions and intermolecular collisions to decrease excited-state energy dissipation. However, most crystal-based organic RTP materials suffer from poor processability, flexibility, and reproducibility, becoming a thorny obstacle to their practical application.Amorphous organic polymers with long-lived RTP characteristics are more competitive in materials science. The intertwined structures and long chains of polymers not only ensure the rigid environment with multiple interactions but also protect triplet excitons from the surroundings, which are conducive to realizing ultralong and bright RTP emission. Exploring the fabrication strategies, intrinsic mechanisms, and practical applications of organic long-lived RTP polymers is highly desirable but remains a formidable challenge. In particular, intelligent organic RTP polymer systems that are capable of dynamically responding to external stimuli (e.g., light, temperature, oxygen, and humidity) have been rarely reported. To develop multifunctional RTP materials and expand their potential applications, a great amount of effort has been expended.This Account gives a summary of the significant advances in amorphous organic RTP polymer systems, especially smart stimulus-responsive ones, focusing on the construction of a rigid environment to suppress nonradiative deactivation by abundant inter/intramolecular interactions. The typical interactions in RTP polymer systems mainly include hydrogen bonding, ionic bonding, and covalent bonding, which can change the molecular electronic structures and affect the energy dissipation channels of the excited states. An in-depth understanding of intrinsic mechanisms and an extensive exploration of potential applications for excitation-dependent color-tunable, ultraviolet (UV) irradiation-activated, temperature-dependent, water-responsive, and circularly polarized RTP polymer systems are distinctly illustrated in this Account. Furthermore, we propose some detailed perspectives in terms of materials design, mechanism exploration, and promising application potential with the hope to provide helpful guidance for the future development of amorphous organic RTP polymers.

Long-Lived Organic Room-Temperature Phosphorescence from Amorphous Polymer Systems.

Host–guest materials with room temperature phosphorescence: Tunable emission color and thermal printing patterns

New Phenothiazine Derivatives That Exhibit Photoinduced Room-Temperature Phosphorescence

Summary Room-temperature phosphorescence (RTP) has received extensive attention in recent years due to its various potential applications. Pure organic RTP materials may overcome the shortcomings of harsh preparation conditions and high toxicity associated with metal complexes and rare-earth-containing materials. Although crystallization strategies can yield rigid environments isolated from oxygen, its inferior processability can significantly limit the corresponding practical applications. Considering their flexibility, stretchability, processability, and thermal stability with flexible long chains and intertwined structures, polymers are an ideal material for achieving RTP and realizing practical applications. In this review, we summarize the latest progress in polymer-based RTP materials, elaborating on two strategies of chemical bonding and physical blending. In the last part of the review, challenges and perspectives of amorphous polymers are proposed to improve RTP performance and develop new applications.

Room-temperature phosphorescence from metal-free polymer-based materials

The research of purely organic room-temperature phosphorescence (RTP) materials has drawn great attention for their wide potential applications. Besides single-component and host-guest doping systems, the self-doping with same molecule but different conformations in one state is also a possible way to construct RTP materials, regardless of its rare investigation. In this work, twenty-four phenothiazine derivatives with two distinct molecular conformations were designed and their RTP behaviors in different states were systematically studied, with the aim to deeply understand the self-doping effect on the corresponding RTP property. While the phenothiazine derivatives with quasi-axial (ax) conformation presented better RTP performance in aggregated state, the quasi-equatorial (eq) ones were better in isolated state. Accordingly, the much promoted RTP performance was achieved in the stimulated self-doping state with ax-conformer as host and eq-one as guest, demonstrating the significant influence of self-doping on RTP effect.

Yanxiang Gong

Papers

Host–guest materials with room temperature phosphorescence: Tunable emission color and thermal printing patterns

New Phenothiazine Derivatives That Exhibit Photoinduced Room-Temperature Phosphorescence

Room-temperature phosphorescence from metal-free polymer-based materials

The Effect of Molecular Conformations and Simulated "Self-Doping" in Phenothiazine Derivatives on Room-Temperature Phosphorescence.

The key role of molecular aggregation in rechargeable organic cathodes