Carbon dots confined in 3D polymer network: Producing robust room temperature phosphorescence with tunable lifetimes

Room temperature phosphorescence(RTP) is important in both organic electronics and encryption. Despite rapid advances, a universal approach to robust and tunable RTP materials based on amorphous polymers remains a formidable challenge. Here, we present a strategy that uses three-dimensional(3 D)confinement of carbon dots in a polymer network to achieve ultra-long lifetime phosphorescence. The RTP of the as-obtained materials was not quenched in different polar organic solvents and the lifetime o...     

Aggregation-Enhanced Room-Temperature Phosphorescence from Au(I) Complexes Bearing Mesogenic Biphenylethynyl Ligands

Gold(I) complexes, enabling to form linear coordination geometry, are promising materials for manifesting both aggregation-induced emission (AIE) behavior due to strong intermolecular Au–Au (aurophilic) interactions and liquid crystalline (LC) nature depending on molecular geometry. In this study, we synthesized several gold(I) complexes with rod-like molecular skeletons where we employed a mesogenic biphenylethynyl ligand and an isocyanide ligand with flexible alkoxyl or alkyl chains. The AIE behavior and LC nature were investigated experimentally and computationally. All synthesized gold(I) complexes exhibited AIE properties and, in crystal, room-temperature phosphorescence (RTP) with a relatively high quantum yields of greater than 23% even in air. We have demonstrated that such strong RTP are drastically changed depending on the crystal-size and/or crystal growth process that changes quality of crystals as well as the aggregate structure, of e.g., Au–Au distance. Moreover, the complex with longer flexible chains showed LC nature where RTP can be observed. We expect these rod-like gold(I) complexes to have great potential in AIE-active LC phosphorescent applications such as linearly/circularly polarizing phosphorescence materials.     

Influence of the alkyl side chain length on the room-temperature phosphorescence of organic copolymers

Pure organic room-temperature phosphorescence(RTP) materials have attracted wide attention owing to their excellent luminescent properties and great potential in various applications. In this work, iminostilbene and its analogues are applied to realize RTP emission by copolymerizing with acrylamide. It can be concluded that the growth of alkane chain in monomers can enhance the lifetime and photoluminescence quantum yield of RTP emission, and polymers with the larger conjugated structure of the ...     

“Solid-Liquid” Vitrimers Based on Dynamic Boronic Ester Networks

The "solid-liquid" behavior of vitrimers have not been systematically investigated. Herein, a series of "solid-liquid" vitrimers bearing varying contents of dynamic boronic ester bonds were synthesized via thiol-ene click reactions. These vitrimers allow for flexibile modulation of their network structures and thus show a range of intriguing properties including high stretchability, flexible transition from elasticity to plasticity, strong strain rate dependence, and solid-liquid performance. The dynamic association rate of boronic ester bonds within these vitrimers could be apparently accelerated via increasing the content of boronic ester, which could be used to shape-program the flat vitrimer films into various complex 3 D structures just with external force. Materials with such versatile dynamic behavior may open up a range of new applications.     

A gelable pure organic luminogen with fluorescence-phosphorescence dual emission

Pure organic luminogens with room temperature phosphorescence(RTP) have drawn much attention due to their fundamental importance and promising applications in optoelectronic devices, bioimaging, sensing, etc. Fluorescence-phosphorescence dual emission at room temperature, however, is rarely observed in pure organic materials. Herein, we reported a metal-and heavy-atom free pure organic luminogen with tert-butyl groups, DtBuCZBP, which is ready to form organogels in dimethylsulfoxide(DMSO).It emits prompt and delayed fluorescence, as well as RTP, namely dual emission in as-prepared solid, gels and polymeric films.To the best of our knowledge, it is the first example of metal-and heavy-atom free pure organic gelator with RTP emission. Such unique RTP and moreover dual emission properties in different states make DtBuCZBP a potential material for diverse applications.     

Stimuli-Responsive Polymers with Room-Temperature Phosphorescence

Taking advantages of the impressing behaviors of room-temperature phosphorescence (RTP), the explorations in RTP materials are not only limited to efficient emission and ultralong lifetime of phosphorescence. The discovery and creation of stimuli-responsive properties have become the major pursuit, which will lay a solid foundation for future applications in RTP materials. Based on this, a review centered on recent progress of stimuli-responsive RTP materials is summarized to show frontier development in polymer systems. Different kinds of stimuli-responsive factors including light, oxygen, temperature, mechanical force and pH regulations are investigated in this review. Many potential applications and promising strategies are deeply discussed with the hope to assist future studies in this area.     

Generation of color-controllable room-temperature phosphorescence via luminescent center engineering and in-situ immobilization

Materials with controllable luminescence colors are highly desirable for numerous promising applications, however, the preparation of such materials, particularly with color-controllable room-temperature phosphorescence (RTP), remains a formidable challenge. In this work, we reported on a facile strategy to prepare color-controllable RTP materials via the pyrolysis of a mixture containing 1-(2-hydroxyethyl)-urea (H-urea) and boric acid (BA). By controlling the pyrolysis temperatures, the as-prepared materials exhibited ultralong RTP with emission colors ranging from cyan, green, to yellow. Further studies revealed that multiple luminescent centers formed from H-urea, which were in-situ embedded in the B₂O₃ matrix (produced from BA) during the pyrolysis process. The contents of the different luminescent centers could be regulated by the pyrolysis temperatures, resulting in color-tunable RTP. Significantly, the luminescent center engineering and in-situ immobilization strategy not only provided a facile method for conveniently preparing color-controllable RTP materials, but also endowed the materials prepared at relatively lower temperatures with color-changeable RTP features under thermal stimulus. Considering their unique properties, the potential applications of the as-obtained materials for advanced anti-counterfeiting and information encryption were preliminarily demonstrated.     

Tough,Reprocessable, and Recyclable Dynamic Covalent Polymers with Ultrastable Long-Lived Room-Temperature Phosphorescence

Room-temperature phosphorescence (RTP) polymers, whose emission can persist for a long period after photoexcitation, are of great importance for practical applications. Herein, dynamic covalent boronic ester linkages with internal B−N coordination are incorporated into a commercial epoxy matrix. The reversible dissociation of B−N bonds upon loading provides an efficient energy dissipation pathway for the epoxy network, while the rigid epoxy matrix can inhibit the quenching of triplet excitons in boronic esters. The obtained polymers exhibit enhanced mechanical toughness (12.26 MJ m⁻³), ultralong RTP (τ=540.4 ms), and shape memory behavior. Notably, there is no apparent decrease in the RTP property upon prolonged immersion in various solvents because the networks are robust. Moreover, the dynamic bonds endow the polymers with superior reprocessablity and recyclability. These novel properties have led to their potential application for information encryption and anti-counterfeiting.     

Organic Room Temperature Phosphorescence Materials for Biomedical Applications

Organic room temperature phosphorescence (RTP) materials have drawn increasing attention due to their unique features, especially the long emission lifetime for applications in biomedicine. In this review, we provide an overview of the recent developments of organic RTP materials applied in the biomedicine field. First, we introduce the basic mechanism of phosphorescence and subsequently we present various strategies of modulating the lifetime and efficiency of room temperature organic phosphorescence. Next, we summarize the progress of organic RTP materials in biological applications, including bioimaging, anti‐cancer and antibacterial therapies. Finally, we provide an outlook with regard to the challenges and future perspectives in the field.     

Towards Scalable Fabrications and Applications of 2D Layered Material-based Vertical and Lateral Heterostructures

Among 108423 unique, experimentally known 3D compounds, there exist 1825 ones that are either easily or potentially exfoliable. This increasingly broad library of 2D layered materials(2DLMs) with variable physical properties as well as the unique ability to vertical stacking or lateral stitching 2DLMs into complex heterostructures enables a new dimension for materials engineering and device design, offering novel functional electronics and optoelectronics for flexible industry. In this review, we present a comprehensive summary of the state-of-the-art scalable fabrication technologies, the unique properties as well as the potential device applications of the emerging 2D heterostructures. Firstly, we depict an overall picture of the 2D vertical van der Waals heterostructures. Secondly, we focus on the 2D lateral heterostructures by CVD technique. For a quick access and full coverage, both the vertical and lateral 2D heterostructures are classified into several types according to their chemical compounds with different dimensions. In the end, both the challenges and potential applications of these 2D heterostructures are discussed.     

Multi-stimulus Room Temperature Phosphorescent Polymers Sensitive to Light and Acid cyclically with Energy Transfer

The stimulus-responsive room temperature phosphorescent (RTP) materials have endowed wide potential applications. In this work, by introducing naphthalene and spiropyran (SP) into polyacrylamide as the energy donor and acceptor respectively, a new kind of brilliant dynamic color-tunable amorphous copolymers were prepared with good stability and processibility, and afterglow emissions from green to orange in response to the stimulus of photo or acid, thanks to multi-responsibility of SP and the energy transfer between naphthalene and SP. In addition to the deeply exploring of the inherent mechanism, these copolymers have been successfully applied in dynamically controllable applications in information protection and delivery.     

A novel metal-free amorphous room-temperature phosphorescent polymer without conjugation

Room-temperature phosphorescence(RTP) has attracted much attention due to its potential applications in the fields of biological imaging, chemical sensors and so forth. Particularly, amorphous metal-free RTP materials show special advantages of low cost and good processability. In addition, non-conjugated polymers have seldom been reported as phosphorescent materials.In this work, a novel non-conjugated amorphous metal-free copolymer composed of brominated olefins and acrylamide was prepared in a facile way, which could engender blue-purple RTP emission. Polymers with different kinds of brominated olefins and different ratios of two monomers have been investigated with the purpose of researching the composition/property relationship that may affect the RTP properties. This unique phenomenon could be due to the clustering of carbonyl and amino units caused molecular interaction, and the heavy-atom effect enhanced intersystem crossing. Meantime, the hydrogen bonding in the system enhanced the conformation rigidification to reduce the non-radiative decay. This work provided a delicate way to construct non-conjugated metal-free RTP materials and supplied a new insight into the development of RTP materials.     

Achieving White-Light Emission Using Organic Persistent Room Temperature Phosphorescence

Artificial lighting currently consumes approximately one-fifth of global electricity production. Organic emitters with white persistent RTP have potential for applications in energy-efficient lighting technologies, due to their ability to harvest both singlet and triplet excitons. Compared to heavy metal phosphorescent materials, they have significant advantages in cost, processability, and reduced toxicity. Phosphorescence efficiency can be improved by introducing heteroatoms, heavy atoms, or by incorporating luminophores within a rigid matrix. White-light emission can be achieved by tuning the ratio of fluorescence to phosphorescence intensity or by pure phosphorescence with a broad emission spectrum. This review summarizes recent advances in the design of purely organic RTP materials with white-light emission, describing single-component and host-guest systems. White phosphorescent carbon dots and representative applications of white-light RTP materials are also introduced.     

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

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.     

Engineering Flexible Metal-Phenolic Networks with Guest Responsiveness via Intermolecular Interactions

Flexible metal-organic materials are of growing interest owing to their ability to undergo reversible structural transformations under external stimuli. Here, we report flexible metal-phenolic networks (MPNs) featuring stimuli-responsive behavior to diverse solute guests. The competitive coordination of metal ions to phenolic ligands of multiple coordination sites and solute guests (e.g., glucose) primarily determines the responsive behavior of the MPNs, as revealed experimentally and computationally. Glucose molecules can be embedded into the dynamic MPNs upon mixing, leading to the reconfiguration of the metal-organic networks and thus changes in their physicochemical properties for targeting applications. This study expands the library of stimuli-responsive flexible metal-organic materials and the understanding of intermolecular interactions between metal-organic materials and solute guests, which is essential for the rational design of responsive materials for various applications.     

Organic Nanocrystals with Bright Red Persistent Room‐Temperature Phosphorescence for Biological Applications

Persistent room‐temperature phosphorescence (RTP) in pure organic materials has attracted great attention because of their unique optical properties. The design of organic materials with bright red persistent RTP remains challenging. Herein, we report a new design strategy for realizing high brightness and long lifetime of red‐emissive RTP molecules, which is based on introducing an alkoxy spacer between the hybrid units in the molecule. The spacer offers easy Br−H bond formation during crystallization, which also facilitates intermolecular electron coupling to favor persistent RTP. As the majority of RTP compounds have to be confined in a rigid environment to quench nonradiative relaxation pathways for bright phosphorescence emission, nanocrystallization is used to not only rigidify the molecules but also offer the desirable size and water‐dispersity for biomedical applications.     

Visible-light-excited long-lived organic room-temperature phosphorescence of phenanthroline derivatives in PVA matrix by H-bonding interaction for security applications

Organic room-temperature phosphorescence (RTP) materials are very attractive, but there is still a challenge to achieve RTP for their practical applications under visible light excitation (λ > 400 nm) because of the implement for the most organic RTP is under ultraviolet light. Herein, a simple tactics for inhibiting the vibrational dissipation of three amorphous phenanthroline derivatives by doping them into polyvinyl alcohol (PVA) matrix was utilized to afford visible-light excitation RTP. By using this method, on account of the mutual H-bonding and confinement effect with PVA matrix, a series of organic RTP materials with blue-green phosphorescence emission were obtained under visible-light excitation. The afterglow colors of RTP materials can be adjusted by co-doping the available fluorescence dyes (RhB or Rh6G) into the PVA films through a triplet-to-singlet Förster resonance energy transfer. However, the H-bonding is easily broken by water molecules resulting in the RTP phenomenon disappears. Hence, Aphen-epoxy resin composite system was constructed to overcome this drawback. It is shown that the composite still has good phosphorescence properties after soaking in water for 7 days. The superior RTP of the amorphous phenanthroline derivatives in processable polymer matrices endows these materials with a highly potential for the night warning clothing coating and information encryption.     

Induction of Strong Long‐Lived Room‐Temperature Phosphorescence of N‐Phenyl‐2‐naphthylamine Molecules by Confinement in a Crystalline Dibromobiphenyl Matrix

The design and preparation of metal‐free organic materials that exhibit room‐temperature phosphorescence (RTP) is a very attractive topic owing to potential applications in organic optoelectronic devices. Herein, we present a facile approach to efficient and long‐lived organic RTP involving the doping of N‐phenylnaphthalen‐2‐amine (PNA) or its derivatives into a crystalline 4,4′‐dibromobiphenyl (DBBP) matrix. The resulting materials showed strong and persistent RTP emission with a quantum efficiency of approximately 20 % and a lifetime of a few to more than 100 milliseconds. Bright white dual emission containing blue fluorescence and yellowish‐green RTP from the PNA‐doped DBBP crystals was also confirmed by Commission Internationale de l'Eclairage (CIE) coordinates of (x=0.29–0.31, y=0.38–0.41).     

Disorder-Enhanced Charge-Transfer-Mediated Room-Temperature Phosphorescence in Polymer Media

Room-temperature phosphorescence (RTP) polymers have important applications for biological imaging, oxygen sensing, data encryption, and photodynamic therapy. Despite the many advantages polymeric materials offer such as great control over gas permeability and processing flexibility, disorder is traditionally considered as an intrinsic negative impact on the efficiency for embedded RTP luminophores, as various allowed thermal motions could quench the emitting states. However, we propose that such disorder-enabled freedoms of microscopic motions can be beneficial for charge-transfer-mediated RTP, which is facilitated by molecular conformational changes among different electronic transition states. Using the “classic” pyrene-aniline exciplex as an example, we demonstrate the mutual enhancement of red/near-infrared and green RTP emissions from the pyrene and aniline moieties, respectively, upon doping the aniline polymer with trace pyrene derivatives. In comparison, a pyrene-doped crystal formed with the same aniline structure exhibits only charge-transfer fluorescence with no red or green RTP observed, suggesting that order suppresses the RTP channels. The proposed polymerization strategy may be used as a unified method to generate multi-emissive polymeric RTP materials from a vast pool of known and unknown exciplexes and charge-transfer complexes.     

Enhanced Room-Temperature Phosphorescence through Intermolecular Halogen/Hydrogen Bonding

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.