Amorphous Ionic Polymers with Color‐Tunable Ultralong Organic Phosphorescence

Amorphous purely organic phosphorescence materials with long‐lived and color‐tunable emission are rare. Herein, we report a concise chemical ionization strategy to endow conventional poly(4‐vinylpyridine) (PVP) derivatives with ultralong organic phosphorescence (UOP) under ambient conditions. After the ionization of 1,4‐butanesultone, the resulting PVP‐S phosphor showed a UOP lifetime of 578.36 ms, which is 525 times longer than that of PVP polymer itself. Remarkably, multicolor UOP emission ranging from blue to red was observed with variation of the excitation wavelength, which has rarely been reported for organic luminescent materials. This finding not only provides a guideline for developing amorphous polymers with UOP properties, but also extends the scope of room‐temperature phosphorescence (RTP) materials for practical applications in photoelectric fields.     

Cyclic Triimidazole Derivatives: Intriguing Examples of Multiple Emissions and Ultralong Phosphorescence at Room Temperature

The performance of solid luminogens depends on both their inherent electronic properties and their packing status. Intermolecular interactions have been exploited to achieve persistent room‐temperature phosphorescence (RTP) from organic molecules. However, the design of organic materials with bright RTP and the rationalization of the role of interchromophoric electronic coupling remain challenging tasks. Cyclic triimidazole has been shown to be a promising scaffold for such purposes owing to its crystallization‐induced room‐temperature ultralong phosphorescence (RTUP), which has been associated with H‐aggregation. Herein, we report three triimidazole derivatives as significant examples of multifaceted emission. In particular, dual fluorescence, RTUP, and phosphorescence from the molecular and supramolecular units were observed. H‐aggregation is responsible for the red RTUP, and Br substituents favor yellow molecular phosphorescence while halogen‐bonded Br⋅⋅⋅Br tetrameric units are involved in the blue‐green phosphorescence.     

A metal-free 2D layered organic ammonium halide framework realizing full-color persistent room-temperature phosphorescence

Organic–inorganic hybrid metal halides have attracted intensive attention because of their unique electronic structure and solution processability. They have a rigid micro/nano-structure and heavy atom effect, which has obvious advantages in promoting organic room temperature phosphorescence (RTP). However, the toxicity of heavy metals has limited their further development. Herein, two metal-free 2D layered ammonium halides, homopiperonylammonium bromide and chloride (HLB and HLC), are described for the first time. Their layered structure consists of rigid inorganic ammonium halide laminates and neatly stacked organic layers. The rigid laminates and external heavy atom effect of halogen atoms make HLB and HLC produce green RTP. When phosphor guests with different triplet energies are doped into HLB, HLC, or phenylethylamine salt hosts, effective full-color and even white ultra-long RTP with phosphorescence quantum yield up to 18.7% and lifetime up to 1.7 s is realized through energy transfer between the host and guest. Due to the simple solution synthesis, 10 g-level doped layered organic ammonium halides with the same phosphorescence properties can be easily obtained. The information ink based on these doped halides and non-toxic ethanol solvent can form various patterns on filter paper. The fluorescence and phosphorescence of these patterns are sensitive to the excitation wavelength and acid–base vapor. Consequently, they can be applied to multiple complex anti-counterfeiting and fluorescence/phosphorescence dual-mode chemical sensors.

A kind of metal-free organic ammonium halides characterized by a unique 2D layered structure show colorful ultralong phosphorescence. Phosphorescent quantum yield (up to 19%) and lifetime (up to 1.7 s) can be tuned by doping with different phosphors.     

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).     

Recent Advances of Pure Organic Room Temperature Phosphorescence Materials for Bioimaging Applications

Bioimaging,as a powerful and helpful tool,which allows people to investigate deeply within living organisms,has contributed a lot for both clinical theranostics and scientific research.Pure organic room temperature phosphorescence(RTP)materials with the unique features of ultralong luminescence lifetime and large Stokes shift,can efficiently avoid biological autofluorescence and scattered light through a time-resolved imaging modality,and thus are attracting increasing attention.This review classifies pure organic RTP materials into three categories,including small molecule RTP materials,polymer RTP materials and supramolecular RTP materials,and summarizes the recent advances of pure organic RTP materials for bioimaging applications.     

Diboraanthracene-Doped Polymer Systems for Colour-Tuneable Room-Temperature Organic Afterglow

Organic ultralong room temperature phosphorescence (RTP), or organic afterglow, is a unique phenomenon, gaining widespread attention due to its far-reaching application potential and fundamental interest. Here, two laterally expanded 9,10-dimesityl-dihydro-9,10-diboraanthracene (DBA) derivatives are demonstrated as excellent afterglow materials for red and blue-green light emission, which is traced back to persistent thermally activated delayed fluorescence and RTP. The lateral substitution of polycyclic DBA scaffold, together with weak transversal electron-donating mesityl groups, ensures the optimal molecular properties for (reverse) intersystem crossing and long-lived triplet states in a rigid poly(methyl methacrylate) matrix. The achieved afterglow emission quantum yields of up to 3 % and 15 %, afterglow lifetimes up to 0.8 s and 3.2 s and afterglow durations up to 5 s and 25 s (for red and blue-green emitters, respectively) are attributed to the properties of single molecules.     

Solid-State Photochemical Cascade Process Boosting Smart Ultralong Room-Temperature Phosphorescence in Bismuth Halides

Molecular ultralong room-temperature phosphorescence (RTP), exhibiting multiple stimuli-responsive characteristics, has garnered considerable attention due to its potential applications in light-emitting devices, sensors, and information safety. This work proposes the utilization of photochemical cascade processes (PCCPs) in molecular crystals to design a stepwise smart RTP switch. By harnessing the sequential dynamics of photo-burst movement (induced by [2+2] photocycloaddition) and photochromism (induced by photogenerated radicals) in a bismuth (Bi)-based metal-organic halide (MOH), a continuous and photo-responsive ultralong RTP can be achieved. Furthermore, utilizing the same Bi-based MOH, diverse application demonstrations, such as multi-mode anti-counterfeiting and information encryption, can be easily implemented. This work thus not only serves as a proof-of-concept for the development of solid-state PCCPs that integrate photosalient effect and photochromism with light-chemical-mechanical energy conversion, but also lays the groundwork for designing new Bi-based MOHs with dynamically responsive ultralong RTP.     

Stimuli-Responsive Circularly Polarized Organic Ultralong Room Temperature Phosphorescence

Purely organic materials showing room temperature phosphorescence (RTP) and ultralong RTP (OURTP) have recently attracted much attention. However, it is challenging to integrate circularly polarized luminescence (CPL) into RTP/OURTP. Here, we show a strategy to realize CPL-active OURTP (CP-OURTP) by binding an achiral phosphor group directly to the chiral center of an ester chain. Engineering of this flexible chiral chain enables efficient chirality transfer to carbazole aggregates, resulting in strong CP-OURTP with a lifetime of over 0.6 s and dissymmetry factor of 2.3×10⁻³ after the conformation regulation upon photo-activation. The realized CP-OURTP is thus stable at room temperature but can be deactivated quickly at 50 °C to CP-RTP with high CPL stability during the photo-activation/thermal-deactivation cycles. Based on this extraordinary photo/thermal-responsive and highly reversible CP-OURTP/RTP, a CPL-featured lifetime-encrypted combinational logic device has been successfully established.     

Designing Efficient and Ultralong Pure Organic Room‐Temperature Phosphorescent Materials by Structural Isomerism

Pure organic materials with ultralong room‐temperature phosphorescence (RTP) are attractive alternatives to inorganic phosphors. However, they generally show inefficient intersystem crossing (ISC) owing to weak spin–orbit coupling (SOC). A design principle based on the realization of small energy gap between the lowest singlet and triplet states (ΔE_ST) and pure ππ* configuration of the lowest triplet state (T₁) via structural isomerism was used to obtain efficient and ultralong RTP materials. The meta isomer of carbazole‐substituted methyl benzoate exhibits an ultralong lifetime of 795.0 ms with a quantum yield of 2.1 %. Study of the structure–property relationship shows that the varied steric and conjugation effects imposed by ester substituent at different positions are responsible for the small ΔE_ST and pure ππ* configuration of T₁.     

Ultralong organic room-temperature phosphorescence of electron-donating and commercially available host and guest molecules through efficient F?rster resonance energy transfer

Ultralong organic room-temperature phosphorescence(RTP) materials have attracted tremendous attention recently due to their diverse applications. Several ultralong organic RTP materials mimicking the host-guest architecture of inorganic systems have been exploited successfully. However, complicated synthesis and high expenditure are still inevitable in these studies. Herein, we develop a series of novel host-guest organic phosphorescence systems, in which all luminophores are electron-rich, commercially available and halogen-atom-free. The maximum phosphorescence efficiency and the longest lifetime could reach 23.6% and 362 ms, respectively. Experimental results and theoretical calculation indicate that the host molecules not only play a vital role in providing a rigid environment to suppress non-radiative decay of the guest, but also show a synergistic effect to the guest through F?rster resonance energy transfer(FRET). The commercial availability, facile preparation and unique properties also make these new host-guest materials an excellent candidate for the anti-counterfeiting application. This work will inspire researchers to develop new RTP systems with different wavelengths from commercially available luminophores.     

9,9-Dimethylxanthene Derivatives with Room-Temperature Phosphorescence: Substituent Effects and Emissive Properties

Room-temperature phosphorescence (RTP) emitters with ultralong lifetimes are emerging as attractive targets because of their potential applications in bioimaging, security, and other areas. But their development is limited by ambiguous mechanisms and poor understanding of the correlation of the molecular structure and RTP properties. Herein, different substituents on the 9,9-dimethylxanthene core (XCO) result in compounds with RTP lifetimes ranging from 52 to 601 ms, which are tunable by intermolecular interactions and molecular configurations. XCO-PiCl shows the most persistent RTP because of its reduced steric bulk and multiple sites of the 1-chloro-2-methylpropan-2-yl (PiCl) moiety for forming intermolecular interactions in the aggregated state. The substituent effects reported provide an efficient molecular design of organic RTP materials and establishes relationships among molecular structures, intermolecular interactions, and RTP properties.     

Tunable Phosphorescence/Fluorescence Dual Emissions of Organic Isoquinoline-Benzophenone Doped Systems by Alkoxy Engineering

Dual/multi-component organic doped systems with room-temperature phosphorescence (RTP) properties have been developed. However, the unknown luminescence mechanism still greatly limits the development of the doped materials. Herein, a new doped system exhibiting phosphorescence/fluorescence dual emission (Φ_phos=4–24 % and τ_phos=101–343 ms) is successfully constructed through prediction and design. A series of isoquinoline derivatives with different alkoxy chains were selected as the guests. Benzophenone was chosen as the host owing to the characteristics of low melting point and good crystallinity. The alkoxy chain lengths of the guests are first reported to be used to control the fluorescence and phosphorescence intensities of the doped materials, which results in different prompt emission colors. Additionally, the doped ratio of the guest and host can also control the luminous intensities of the materials. In particular, the doped materials still exhibit phosphorescent properties even if the ratio of the guest/host is as low as 1:100 000.     

A Synergistic Enhancement Strategy for Realizing Ultralong and Efficient Room-Temperature Phosphorescence

An enhancement strategy is realized for ultralong bright room-temperature phosphorescence (RTP), involving polymerization between phosphor monomers and acrylamide and host–guest complexation interaction between phosphors and cucurbit[6,7,8]urils (CB[6,7,8]). The non-phosphorescent monomers exhibit 2.46 s ultralong lifetime after copolymerizing with acrylamide. The improvement is due to the rich hydrogen bond and carbonyl within the polymers which promote intersystem crossing, suppress nonradiative relaxation and shield quenchers effectively. By tuning the ratio of chromophores, a series of phosphorescent copolymers with different lifetimes and quantum yields are prepared. The complexation of macrocyclic hosts CB[6,7,8] promote the RTP of polymers by blocking aggregation-caused quenching, and offsetting the losses of aforementioned interaction provided by polymer. Multiple lifetime-encoding for digit and character encryption are achieved by utilizing the difference of their lifetimes.     

Long‐Lived Room‐Temperature Phosphorescence for Visual and Quantitative Detection of Oxygen

An unconventional organic molecule (TBBU) showing obvious long‐lived room temperature phosphorescence (RTP) is reported. X‐ray single crystal analysis demonstrates that TBBU molecules are packed in a unique fashion with side‐by‐side arranged intermolecular aromatic rings, which is entirely different from the RTP molecules reported to date. Theoretical calculations verify that the extraordinary intermolecular interaction between neighboring molecules plays an important role in RTP of TBBU crystals. More importantly, the polymer film doped with TBBU inherits its distinctive RTP property, which is highly sensitive to oxygen. The color of the doped film changes and its RTP lifetime drops abruptly through a dynamic collisional quenching mechanism with increasing oxygen fraction, enabling visual and quantitative detection of oxygen. Through analyzing the grayscale of the phosphorescence images, a facile method is developed for rapid, visual, and quantitative detection of oxygen in the air.     

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.     

Ultralong Phosphorescence from Organic Ionic Crystals under Ambient Conditions

A new type of materials, organic salts in the crystal state, have ultralong organic phosphorescence (UOP) under ambient conditions. The change of cations (NH₄⁺, Na⁺, or K⁺) in these phosphors gives access to tunable UOP colors ranging from sky blue to yellow green, along with ultralong emission lifetimes of over 504 ms. Single‐crystal analysis reveals that unique ionic bonding can promote an ordered arrangement of organic salts in crystal state, which then can facilitate molecular aggregation for UOP generation. Additionally, reversible ultralong phosphorescence can be realized through the alternative employment of fuming gases (ammonia and hydrogen chloride), demonstrating its potential as a candidate for visual ammonic or hydrogen chloride gas sensing. The results provide an environmental responsible and practicable synthetic approach to expanding the scope of ultralong organic phosphorescent materials as well as their applications.     

9,9‐Dimethylxanthene Derivatives with Room‐Temperature Phosphorescence: Substituent Effects and Emissive Properties

Room‐temperature phosphorescence (RTP) emitters with ultralong lifetimes are emerging as attractive targets because of their potential applications in bioimaging, security, and other areas. But their development is limited by ambiguous mechanisms and poor understanding of the correlation of the molecular structure and RTP properties. Herein, different substituents on the 9,9‐dimethylxanthene core (XCO) result in compounds with RTP lifetimes ranging from 52 to 601 ms, which are tunable by intermolecular interactions and molecular configurations. XCO‐PiCl shows the most persistent RTP because of its reduced steric bulk and multiple sites of the 1‐chloro‐2‐methylpropan‐2‐yl (PiCl) moiety for forming intermolecular interactions in the aggregated state. The substituent effects reported provide an efficient molecular design of organic RTP materials and establishes relationships among molecular structures, intermolecular interactions, and RTP properties.     

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...     

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.     

Stimuli‐Responsive Circularly Polarized Organic Ultralong Room Temperature Phosphorescence

Purely organic materials showing room temperature phosphorescence (RTP) and ultralong RTP (OURTP) have recently attracted much attention. However, it is challenging to integrate circularly polarized luminescence (CPL) into RTP/OURTP. Here, we show a strategy to realize CPL‐active OURTP (CP‐OURTP) by binding an achiral phosphor group directly to the chiral center of an ester chain. Engineering of this flexible chiral chain enables efficient chirality transfer to carbazole aggregates, resulting in strong CP‐OURTP with a lifetime of over 0.6 s and dissymmetry factor of 2.3×10^?3 after the conformation regulation upon photo‐activation. The realized CP‐OURTP is thus stable at room temperature but can be deactivated quickly at 50 °C to CP‐RTP with high CPL stability during the photo‐activation/thermal‐deactivation cycles. Based on this extraordinary photo/thermal‐responsive and highly reversible CP‐OURTP/RTP, a CPL‐featured lifetime‐encrypted combinational logic device has been successfully established.