Persistent Room Temperature Phosphorescence from Triarylboranes: A Combined Experimental and Theoretical Study.

Room-temperature phosphorescence (RTP) materials with high efficiency have attracted much attention because they have unique characteristics that cannot be realized in conventional fluorescent materials. Unfortunately, efficient RTP in metal-free organic materials is very rare and it has traditionally been considered as the feature to divide purely organic compounds from organometallic and inorganic compounds. There has been increasing research interest in the design and preparation of metal-free organic RTP materials in recent years. It has been reported that intermolecular interactions make a big difference to the photophysical behavior of organic molecules. In this regard, herein, the parameters that affect RTP efficiency are discussed, and a brief review of recent intermolecular halogen-/hydrogen-bonding strategies for efficient RTP in metal-free organic materials are provided. The opportunities and challenges are finally elaborated in the hope of guiding promising directions for the design and application of RTP materials.

Purely organic room temperature phosphorescence (RTP) materials have shown broad application prospects in organic light‐emitting diodes (OLEDs) due to their theoretical 100% exciton utilization, cost‐effectiveness, and flexibility. In recent years, with the deepening of research, various luminescent mechanisms have been proposed, and RTP materials have made significant progress, which have been effectively applied to OLEDs. This article comprehensively reviews the research progress of RTP materials in OLEDs and introduces the development of a series of high‐efficiency RTP materials from the perspective of molecular design strategies and photophysical properties. These conclusions draw a roadmap to address the inherent challenges in utilizing organic RTP materials to specifically advance the investigation of OLEDs.

Organic room-temperature phosphorescence (RTP) materials with large Stokes shifts and prolonged afterglows are gaining increasing attention in a variety of applications, including displays, anti-counterfeiting, sensing, and bioimaging. However, achieving high-performance organic RTP remains challenging due to weak spin-orbit coupling, rapid non-radiative decay, and unstable triplet excitons. Early studies focused on crystal engineering, as ordered lattices restrict molecular motion and stabilize triplet excitons. Analyzing crystal structures and packing provides valuable insights into intermolecular interactions, while theoretical calculations have clarified electronic structures, laying the foundation for rational RTP material design. However, recent findings suggest RTP in many single-component systems may arise from trace impurities, significantly influencing RTP properties. This discovery has greatly advanced the understanding of impurity-induced phosphorescence. This review systematically examines the role of impurities in RTP, detailing their origins from starting materials, solvents, and side reactions. It also explores how these identified impurities can serve as essential building blocks for designing new RTP materials. Finally, essential methods for evaluating compound purity, emphasizing the critical importance of rigorous analysis and validation are presented. Material purity plays a pivotal role in RTP research, as impurities can distort experimental data, potentially leading to misinterpretations that can impede advancements in understanding the underlying mechanisms.

Pure organic room temperature phosphorescence (RTP) materials are considered as potential candidates for replacing precious metal-based complexes to fabricate highly efficient organic light emitting devices (OLEDs). However, for reported RTP materials, low photoluminescence quantum yields (PLQYs) in thin film state seriously impede their applications in OLEDs. On the other hand, how using normal organic fluorescence materials to fabricate OLEDs with an internal quantum efficiency (IQE) over 25% remains a great unaddressed issue beyond the thermally activated delayed fluorescence (TADF) sensitization approach. Here, we establish a strategy to construct highly efficient OLEDs based on pure organic RTP material sensitized fluorescence emitter. The key point for our strategy is that benzimidazole-triazine molecules (PIM-TRZ), 2,6-di(phenothiazinyl)naphthalene (β-DPTZN) and 5,6,11,12-tetraphenylnaphthacene (rubrene) were screened as host, phosphor sensitizer and fluorescent emitter, respectively. Detail photophysical characterizations demonstrate that the host material PIMTRZ with unique RTP nature is critical for achieving phosphor sensitizing process. As an organic RTP compound, the singlet and triplet state energy levels of β-DPTZN perfectly match with those of PIMTRZ, resulting in the formation and lasting existence of phosphor’s excitons in emitting layer. The large overlap between the absorption spectrum of rubrene and PL spectrum of PIM-TRZ:10% β-DPTZN film can facilitate the Förster energy transfer from the triplet β-DPTZN to the singlet rubrene and the finally displayed fluorescence is derived from singlet excited states of rubrene. The perfect collocation of host, phosphorescent sensitizer and fluorescent emitter in the emitting layer promise the predominant performance of the devices with external quantum efficiency (EQE) of 15.7%. The PLQY of emitting layer is 60.3%, and therefore about 90% carrier injection induced excitons are harvested for light emission. We present a new strategy to fabricate efficient fluorescent devices by employing ingenious combination of host, phosphorescent sensitizer and fluorescent emitter, which is significant to the development of OLEDs.

Long-lived room temperature phosphorescence (RTP) materials are promising for applications in various fields including security information, medical diagnostics, and molecular imaging because of their unique optical properties. Previous RTP materials are mainly excited by ultraviolet light, while synthesizing long-lived RTP materials with visible-light-excitation remains a challenge. In particular, long-lived RTP materials that can be excited by green light are rare. Herein, a feasible and concise chemical strategy for constructing hydrogen-bonded frameworks in an aqueous environment is developed to fabricate large-size, green-light-excited, and excitation-dependent long-lived RTP carbon dot crystals (m,p/CDs-ME). The RTP performance of the crystals exhibits strong excitation wavelength dependence, leading to a full range of visible-light tuning from blue to red. Importantly, the maximum excitation wavelength of the RTP crystals is around 500 nm, thus successfully realizing green light excitation. m,p/CDs-ME presents long-lived phosphorescence (130 ms) under 500 nm excitation in aqueous solution, making it highly suitable for dopamine detection. This work not only provides a general guideline for the development of large size long-lived RTP crystals but also extends the operation scope of long-lived RTP materials in the detection of biomarkers by visible light excitation.

Ultralong sodium alginate-based room temperature phosphorescence materials with advantages of color tunability, flexibility and facile large-area fabrication

Developing metal-free and long lifetime room-temperature phosphorescence (RTP) materials has received tremendous interest due to their numerous potential applications, of which stable triplet-excited state is the core challenge. Here, boron carbon oxynitride (BCNO) dots, emitting stable blue fluorescence and green RTP, are reported for the first time. The obtained BCNO dots exhibit an unexpected ultralong RTP lifetime of 1.57 s, lasting over 8 s to naked eyes. The effective doping of carbon and oxygen elements in boron nitride (BN) actually provides a small energy gap between singlet and triplet states, facilitating the intersystem crossing (ISC) and populating of triplet excitons. The formation of compact cores via crystallization and effective inter-/intra-dot hydrogen bonds further stabilizes the excited triplet states and reduces quenching of RTP by oxygen at room temperature. Based on the water-soluble feature of BCNO dots, a novel advanced security ink is developed toward anti-counterfeiting tag and confidential information encryption. This study extends BCNO dots to rarely exploited phosphorescence fields and also provides a facile strategy to prepare ultralong lifetime metal-free RTP materials.

Polymer carbon dots (PCDs) are proposed as a new class of room-temperature phosphorescence (RTP) materials. The abundant energy levels in PCDs increase the probability of intersystem crossing (ISC) and their covalently crosslinked framework structures greatly suppress the nonradiative transitions. The efficient methods allow the manufacture of PCDs with unique RTP properties in air without additional metal complexation or complicated matrix composition. They thus provide a route towards the rational design of metal-free RTP materials that may be synthesized easily. Furthermore, we find that RTP is associated with a crosslink-enhanced emission (CEE) effect, which provides further routes to design improved PCDs with diverse RTP performance. Our results show the potential of PCDs as a universal route to achieve effective metal-free RTP.

This minireview focuses on recent advancements in organic molecular-to-supramolecular self-assembled room-temperature phosphorescent (RTP) materials and their prospective biomedical applications. RTP materials, having their unique capacity to emit long-lasting phosphorescence at ambient temperature, have piqued researchers' interest in various biological applications, including biosensing, bioimaging, drug delivery, and photodynamic therapy (PDT). These materials have several benefits, including high sensitivity, remarkable photostability, and low cytotoxicity. RTP materials' self-assembly into supramolecular structures improves their performance and broadens their uses. Researchers have built organic RTP systems with long-lasting phosphorescence by leveraging weak noncovalent interactions in aquatic conditions. These materials have demonstrated incredible promise as biosensors that enable sensitive analyte detection and as photosensitizers in PDT that target and sensitize specific cell types. The review also outlines future directions and challenges in developing and utilizing pure organic RTP materials for biological imaging purposes, providing valuable guidelines for their future design and application.

Polymeric room-temperature phosphorescence (RTP) materials have attracted much attention due to their advantages of easy processing and excellent luminescent properties. However, it is still a challenge to obtain industrial production grade material through simple and green processing strategies. Herein, through the codoping strategy, different phosphors were embedded into nylon, a kind of polymer matrix, to obtain a series of highly efficient RTP materials without any organic solvents, for which the phosphorescence lifetime and brightness could reach 628.8 ms and 14 cd/m2, respectively. Besides, we found that the photophysical properties of these RTP materials varied greatly among different types of nylon matrix, owing to the divergence in the number of hydrogen bonding "sites". The superiority of the injection molding processing strategy enables the preparation of RTP materials to achieve desolvation, which could also be processed into any complex and desiring shape. Significantly, nylon can affect molecular chain changes due to aging and other problems, so that these RTP materials are considered as potential nondestructive testing for nylon product aging levels. This strategy also paves the way for the development of large-scale, eco-friendly, and practical application RTP materials and provides new ideas to industrialized preparation of long-lived RTP materials in the future.

Long‐persistence room temperature phosphorescent (RTP) materials have extensive applications in advanced information encryption, anti‐counterfeiting, and optoelectronic devices. Carbon dots (CDs), as an emerging nano‐luminescent material, are promising candidates for long‐persistence RTP due to their superior optical properties, low cost, minimal toxicity, and high stability. In this study, full‐color, long‐persistence phosphorescent materials are developed via a simple one‐step hydrothermal method using p‐hydroxybenzoic acid (p‐HBA) as a precursor, by reacting with aromatic amines with different degrees of conjugation (o‐phenylenediamine, 9,10‐diaminophenanthrene, 1,8‐diaminonaphthalene, and 1‐aminopyrene). This approach achieves phosphorescence spanning a wavelength range from 432 to 601 nm, in which the longest RTP lifetime is 2.8 s and up to 23 s in the naked eye, without the need for organic materials using fluorescence resonance energy transfer. This is accomplished by modulating the graphite‐N content and degree of conjugation of the CDs, as well as leveraging the dual‐confinement of the B2O3 matrix. These materials exhibit robust long‐persistence phosphorescence stability at room temperature in both organic solvents and cyclic excitation. Based on the excellent constant RTP performance and cyclic stability of the four composites, they can be widely used in advanced information encryption, anti‐counterfeiting, and ASCII code information storage practical applications.

Review: [41 refs.

A novel group of N,N-diaryl-1,2-benzenediamine room temperature phosphors based on structural engineering

Theoretical studies on benzonitrile-carbazole-based pure organic molecules with room-temperature phosphorescence

Room temperature phosphorescence (RTP) materials are increasingly recognized for their superior luminescent properties, which are pivotal in applications such as anti-counterfeiting, information storage, and optoelectronics. Despite this, the sensitivity of most RTP systems to humidity presents a significant challenge in achieving durable RTP performance in aqueous environments. This study proposes a strategy to enhance organic room-temperature phosphorescence through racemization. By incorporating external racemates of various chiral phosphors-NDBD-Ph, NDBD-Ph-Ph, NDBD-CH3, and NDBD-O-CH3-into a polyacrylonitrile (PAN) matrix, we significantly enhance the RTP properties (quantum yield, lifetime, and afterglow-time) of the resultant films. This enhancement can be attributed to the increased density of racemic molecules in the matrix and the increased spin-orbit coupling (SOC), facilitating the development of a long-lasting polymer RTP system in water. Notably, the racemic rac-NDBD-Ph@PAN film exhibits a persistent bright turquoise afterglow, even after immersion in water for a month. Furthermore, for the first time, we achieved an enhanced green to cyan RTP response to pH variations under both acidic and alkaline conditions (pH = 2-12), with the maximum phosphorescence emission intensity increasing up to threefold. The remarkable water stability, reversible response characteristics, and enhanced phosphorescence properties of this system offer promising potential for dynamic information encryption in aqueous environments.