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As emerging carbon‐based nanomaterials, carbon dots (CDs) are widely studied with regard to their luminescent properties. CDs obtained by the bottom‐up method exhibit polymeric characteristics after crosslinking, polymerization, and incomplete carbonization processes, herein referred to as carbonized polymer dots (CPDs). In recent years, large progress has been achieved on the room‐temperature phosphorescence (RTP) properties of CPDs. The developments and synthesis strategies for RTP CPD materials are reviewed. However, less attention has been devoted to the influence of polymeric structures on RTP of CPD materials. Polymer structures are a common feature of CPD materials. The extensive polymer structures are the key factors facilitating the RTP of CPD materials. Herein, the effects of the polymer structures on the RTP emission of self‐protective CPD and matrix‐assisted CPD materials are discussed. It is considered that the polymer structures can effectively immobilize subluminophores and protect triplet excited states to facilitate the RTP emission of CPD materials. The crosslink‐enhanced emission (CEE) effect is proposed to further explain the RTP emission of CPD materials, which can provide an effective strategy to immobilize CPDs. Benefiting from CEE effect, efficient RTP can be achieved for CPD materials. The applications of CPD materials are then briefly summarized.

The 1H-benzo[f]indole (Bd[f]), a carbazole (Cz) isomer is first reported as the source of Cz-based phosphors in 2020. In this work, the novel carbazole isomers, 1H-benzo[g]indole (Bd[g]) based derivatives, are synthesized by a one-step solvent-free mechanical ball milling reaction, establishing a facile, efficient, and environmentally friendly method for the synthesis of new Cz isomer phosphorescent derivatives with high yields compared to previously reported multi-step solvent-based thermochemical synthesis routes of Bd[f] derivatives with low yields. Six Bd[g] derivatives with different substituents, namely OCH 3 -Bd, In-Bd, Bn-Bd, F-Bd, Cl-Bd, and Br-Bd, are synthesized, which exhibit distinctly different single-crystal structures and phosphorescent properties. After irradiation with 365 nm UV light, Bd[g] derivatives-doped poly (methyl methacrylate) (PMMA) films exhibit photoactivated green room-temperature phosphorescence with ultra-long lifetimes up to 1.65 s. Interestingly, the phosphorescence is stable in seawater along with good bactericidal properties, which also provide new candidates for indole-based marine antifoulants. This study demonstrates that mechanical ball milling is an efficient method for the synthesis of benzoindole heterocycles. Bd[g], as new members of the benzoindole family, are new building units to construct carbazole isomer phosphorescent molecules besides Bd[f]., (© 2024 Wiley‐VCH GmbH.)

The exploration of circularly polarized luminescence is important for advancing display and lighting technologies. Herein, by utilizing isomeric molecular engineering, a novel series of chiral molecules are designed to exploit both thermally activated delayed fluorescence (TADF) and room-temperature phosphorescence (RTP) mechanisms for efficient luminescence. The cooperation of a small singlet-triplet energy gap, moderate spin-orbital coupling (SOC), and large oscillator strength enables efficient TADF emission, with photoluminescence quantum yields exceeding 90 %. By altering the symmetry of molecular structures, it is demonstrated that the intrinsic electronic SOC and vibrational SOC effects can be greatly enhanced to facilitate RTP emission. Notably, through modulating simultaneous TADF and RTP emissions, single-molecule white emission is successfully achieved. Accordingly, the TADF-based organic light-emitting diode (OLED) achieves a maximum external quantum efficiency up to 30 %, representing exceptional performance of non-aromatic amine-based emitters. Furthermore, the first single-molecule white OLED based on TADF and RTP dual-emissive chiral material is developed, establishing a benchmark for the development of advanced display and lighting technologies., (© 2024 Wiley-VCH GmbH.)

The development of organic afterglow materials has garnered significant attention due to their diverse applications in smart devices, optoelectronics, and bioimaging. However, polymeric afterglow materials often suffer from short emission lifetimes, typically ranging from milliseconds to seconds, posing a significant challenge for achieving hour-long afterglow (HLA) polymers. This study presents the successful fabrication of transparent HLA polymers by introducing electron donor/acceptor exciplexes. Employing aromatic polyesters as the polymer electron acceptor and charge reservoirs, the resulting HLA polymers exhibited a remarkable green afterglow that persisted for 12 hours under ambient conditions, representing the longest duration achieved for polymeric afterglow materials to date. Intriguingly, these HLA polymers could be activated solely by sunlight, maintaining a green afterglow for over 6 hours at room temperature in air, which outperformed all previously reported afterglow polymers. The doped polymers exhibited superior flexibility and transparency, making them ideal candidates for flexible display applications. Furthermore, successfully spinning these doped polymers into fibers while retaining their HLA properties opens up exciting possibilities for their use in wearable smart devices., (© 2024 Wiley-VCH GmbH.)

Developing smart materials with tunable high-temperature afterglow (HTA) luminescence remains a formidable challenge. This study presents a metal-free doping system using boric acid as matrix and polycyclic aromatic hydrocarbons as dopants. This composition achieves dynamically tunable afterglow combining a bright blue HTA lasting for over ten seconds even at 150°C and an ultra-long yellow room-temperature phosphorescence below 110°C. The observed HTA is attributed to the thermally released exciton recombination within the dopant molecules, which shows excellent temperature tolerance compared to traditional triplet related phosphorescence and thermally activated delayed fluorescence. The planarity of dopants is extensively investigated playing a pivotal role in modulating Dexter electron transfer (ET) for capturing released electrons and thereby affecting the overall performance of tunable HTA. This work provides an efficient and universal doping strategy to engineer tunable HTA through the synergistic action of thermally releasing electrons, Dexter ET and exciton recombination., (© 2024 Wiley‐VCH GmbH.)

Room temperature phosphorescent (RTP) probes have significant advantages in the field of cellular imaging, as their long lifetimes can prevent interference from the spontaneous fluorescence of organisms. Persulfurated arenes are a typical RTP molecular parent nucleus. However, most of the applied research on them is concentrated in anti-counterfeiting, and relatively few are applied in bioimaging. The molecular structure and structure-property relationship of them applied in bioimaging are still in the exploration stage. In this work, we have designed and synthesized a series of RTP probes with long alkyl chains, all of which can be targeted to mitochondria with good water solubility for mitochondria-targeted imaging. Further, we investigated the effect of alkyl chains on the luminescence properties of these probes, and found that the moderate length of alkyl chains can realize the enhancement of phosphorescence intensity. We believe this finding is of guiding significance for the design of molecular structures in the field of RTP probes., (© 2024 Wiley-VCH GmbH.)

Developing efficiency and long-lived room-temperature phosphorescence (RTP) materials through straightforward methods is highly desired. In this work, a stepwise stabilization strategy was proposed by the coordination and in-situ precipitation reactions among organic precursors, inorganic cation and anions, producing room-temperature phosphorescence materials with high emission efficiency (phosphorescence quantum yield of 45 %). Structural and photophysical characterizations revealed the coordination reaction reduced the energy gaps between singlet and triplet states and stabilized the excited states of the guest molecules. The in-situ precipitation reaction produced a solid matrix, which provided isolated environments for protecting the excitons from quenching. The applications of RTP materials in information encryption were demonstrated. The presented results provided a new clue for producing RTP materials, and extended their applications in wide fields., (© 2024 Wiley-VCH GmbH.)

Developing pure organic materials with ultralong lifetimes and balanced quantum efficiency is attractive but challenging. In this study, we propose a novel strategy to investigate external heavy atoms by linking molecular emitters with halogen through a flexible alkyl chain. X-ray crystal analysis clearly reveal the halogen C-X-π interactions, which can be tuned by halogen donors, as well as the distance and geometry between them. Impressively, DOPTZ-C3Cl featuring a chloride atom as donor, exhibits a balanced long phosphorescence lifetime of 1351 ms and a phosphorescence quantum yield of 10.1 %. We also first demonstrate that Cl can induce more positive effect than heavier halogens (Br and I) on prolonging the lifetime. We envisage that the present study will expedite new molecular design to manipulate the room temperature phosphorescence via external heavy atom effect, and highlight a special C-Cl⋅⋅⋅π interaction for the development of ultralong phosphorescent materials., (© 2024 Wiley-VCH GmbH.)

Scintillators have attracted significant attention due to their wide-ranging applications in both industrial and medical fields. However, one of the ongoing challenges is the efficient utilization of triplet excitons to achieve high radioluminescence efficiency. Here, a series of purely organic phosphors is presented for X-ray scintillation, employing a combined rigid and flexible host-guest doping strategy. The doped crystals exhibit a remarkable maximum phosphorescence efficiency of 99.4% under UV excitation. Furthermore, upon X-ray irradiation, the radioluminescence intensities of the doped phosphors are markedly higher compared to their single-component crystal counterparts. Through systematic investigations, it is demonstrated the crucial role of confining isolated chromophores in enhancing scintillation efficiency. Additionally, a transparent scintillator screen fabricated with the doped phosphor exhibits excellent X-ray imaging performance, achieving a high spatial resolution of 18.0 lp mm -1 . This work not only offers valuable insights into suppressing non-radiative transitions of triplet excitons during scintillation but also opens a new avenue for designing highly efficient purely organic phosphorescent scintillators., (© 2024 Wiley‐VCH GmbH.)

Developing pure organic room-temperature phosphorescent (RTP) hydrogels is important for expanding the practical applications of phosphorescent materials. However, most of the reported RTP hydrogels containing aromatic phosphors suffer from short phosphorescent lifetimes, unstable underwater RTP emissions, and complex preparation processes. Herein, novel nonaromatic RTP hydrogels are prepared by using two types of non-traditional luminescent polymers, sodium alginate and a polymeric carboxylate, which are not RTP emissive or very weakly emissive in aqueous environments. The prepared hydrogels exhibit the following features: I) color-tunable RTP emissions with ultra-long lifetimes up to 451.1 ms, II) excellent anti-swelling properties and stable persistent RTP emission even after being immersed in deionized water for months, III) efficient and large-scale preparation of hydrogel fibers by wet spinning technique. Experiment results and theoretical calculations show that the stable and long-lifetime RTP emissions of the hydrogels originate from the introduction of more nonconventional chromophores which are strongly crosslinked with ionic bonding between carboxylate groups and calcium ions and enhanced through-space interactions between them. This work provides a reliable strategy for designing nonaromatic hydrogels with stable and persistent RTP., (© 2024 Wiley‐VCH GmbH.)

Compact luminophores with long emission wavelengths have aroused considerable theoretical and practical interest. Organics with room-temperature phosphorescence (RTP) are also desirable for their longer lifetimes and larger Stokes shifts than fluorescence. Utilizing the low electronic transition energy intrinsic to thiocarbonyl compounds, electron-withdrawing groups were attached to the 4H-pyran-4-thione core to further lower the excited state energies. The resulting mini-phosphors were doped into suitable polymer matrices. These purely organic, amorphous materials emitted near-infrared (NIR) RTP. Having a molar mass of only 162 g mol -1 , one of the phosphors emitted RTP that peaked at 750 nm, with a very large Stokes shift of 15485 cm -1 (403 nm). Thanks to the good processability of the polymer film, light-emitting diodes (LEDs) with NIR emission were easily fabricated by coating doped polymer on ultraviolet LEDs. This work provides an intriguing strategy to achieve NIR RTP using compact luminophores., (© 2024 Wiley-VCH GmbH.)

Afterglow materials have garnered significant interest due to distinct photophysical characteristics. However, it is still difficult to achieve long afterglow phosphorescence from organic molecules due to aggregation-caused quenching (ACQ) and energy dissipation. In addition, most materials reported so far have long afterglow emission only at room or even low temperatures, and mainly use UV light as an excitation source. In this work, we report a strategy to achieve high temperature long afterglow emission through the assembly of isolated 0D metal-organic cages (MOCs). In which, both ACQ and phosphorescence quenching effects are effectively mitigated by altering the stacking mode of organic chromophores through orthogonally anchoring into the edges of cubic MOCs. Furthermore, improvement in molecular rigidity, promotion of spin-orbit coupling and broadening of the absorption range are achieved through the MOC-engineering strategy. As a result, we successfully synthesized MOCs that can produce afterglow emission even after excitation by WLEDs at high temperatures (380 K). Moreover, the MOCs are capable of generating afterglow emissions when excited by mobile phone flashlight at room temperature. Given these features, the potential applications of MOCs in the visual identification of explosives, information encryption and multicolor display are explored., (© 2024 Wiley-VCH GmbH.)

The synthesis, crystal structure and room-temperature phosphorescence (RTP) of a 2D metal-free inorganic covalent framework ((H 2 en) [B 5 O 8 (OH)], named as CityU-12, and en represents for ethylenediamine) are reported. The precise structure information of CityU-12 has been disclosed through both single-crystal X-ray diffraction (SCXRD) analysis and low-dose high-resolution transmission electron microscopy (LD-HRTEM) study. The SCXRD results show that CityU-12 composes of 2D anionic B─O-based covalent inorganic frameworks with protonated ethylenediamine locating in the pore sites of 2D B─O layers while LD-HRTEM suggests that CityU-12 has an interplanar distance of 0.60 nm for (00 2 ¯ $\bar{2}$ ) crystal plane and 0.60 nm for (10 1 ¯ $\bar{1}$ ) crystal plane. The optical studies show that CityU-12 is an excellent nonconventional RTP material with the emission peak at 530 nm and a lifetime of 1.5 s. The quantum yield is 84.6% and the afterglow time is as long as 2.5 s. This work demonstrates that metal-free B─O frameworks can be promising nonconventional phosphors for RTP., (© 2024 Wiley‐VCH GmbH.)

Purely organic room-temperature phosphorescence (RTP) materials have received intense attention due to their fascinating optical properties and advanced optoelectronic applications. The promotion of intersystem crossing (ISC) and minimalization of nonradiative dissipation under ambient conditions are key prerequisites for realizing high-performance organic RTP; However, the ISC process is generally inefficient for organic fluorogens and the populated triplet excitons are always too susceptible to be well stabilized by conventional means. Particularly, organizing organic fluorophores into compact and ordered entities by supramolecular dynamic interactions has proven to be a newly-emerged strategy to boost the ISC process greatly and suppress the non-radiative relaxations immensely, facilitating the population and stabilization of triplet excitons to access high-performance organic RTP. Consequently, well-defined organic emitters enable robust RTP emission even in the solution state, thus greatly extending the applications. Here, this review is focused on a timely and brief introduction to recent progress in tailoring ordered high-performance RTP emitters by supramolecular dynamic interactions. Their typical preparation strategies, optoelectronic properties, and applications are thoroughly summarized. In the summary section, key challenges and perspectives of this field are highlighted to suggest potential directions for future study., (© 2024 Wiley‐VCH GmbH.)

Polymeric room-temperature phosphorescence (RTP) materials especially multicolor RTP systems hold great promise in concrete applications. A key feature in these applications is a triplet charge transfer transition. Aromatic electron donors and electron acceptors are often essential to ensure persistent RTP. There is much interest in fabricating non-aromatic charge-transfer-mediated RTP materials and it still remains a formidable challenge to achieve color-tunable RTP via charge transfer. Herein, a charge-transfer-mediated RTP material by embedding quinoline derivatives within a non-aromatic polymer matrix such as polyacrylamide (PAM) or polyvinyl alcohol (PVA) is developed. Through-space charge transfer (TSCT) is achieved upon alkali- or heat treatment to realize a long phosphorescence lifetime of up to 629.90 ms, high phosphorescence quantum yield of up to 20.51%, and a green-to-blue afterglow for more than 20 s at room temperature. This color-tunable RTP emerges from a nonaromatic polymer to single phosphor charge transfer that has rarely been reported before. This finding suggests that an effective and simple approach can deliver new color-tunable RTP materials for applications including multicolor display, information encryption, and gas detection., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Nonconventional luminophores have received increasing attention, owing to their fundamental importance, advantages in outstanding biocompatibility, easy preparation, environmental friendliness, and potential applications in sensing, imaging, and encryption. Purely organic molecules with outstanding fluorescence and room-temperature phosphorescence (RTP) have emerged as a new library of benign afterglow agents. However, the cost, toxicity, high reactivity, and poor stability of materials also limit their practical applications. Therefore, some natural products, synthetic compounds, and biomolecules have entered horizons of people. The as-designed exhibits sky blue and green fluorescence emission and green RTP emission (a lifetime of 343 ms and phosphorescence quantum of 15.3%) under air condition. This study presents an organic fluorescence for biological imaging and RTP for anti-counterfeiting and encryption based on amino acids, maleic anhydride and 4-vinylbenzenesulfonic acid sodium salt hydrate. This study provides a strategy for nonconventional luminophores in designing and synthesizing pure organic RTP materials., (© 2024 Wiley‐VCH GmbH.)

Room temperature phosphorescence rarely occurs from pure organic molecules, especially in the solid-state. A strategy for the design of highly emissive organic phosphors is still hard to predict, thus impeding the development of new functional materials with the desired optical properties. Herein, we analyze a family of alkyl and aryl-substituted persulfurated benzenes, the latter representing a class of organic solid-state triplet emitters able to show very high emission quantum yield at room temperature. In this work, we correlate structural parameters with the photophysical properties observed in different experimental conditions (diluted solution, crystalline and amorphous phase at RT and low temperature). Our results, corroborated by a detailed computational analysis, indicate a close relationship between the luminescence properties and i) the nature of the substituents on the persulfurated core, ii) the adopted conformations in the solid state, both in crystalline and amorphous phases. These factors contribute to characterize the lowest-energy lying excited-state, its deactivation pathways, the phosphorescence lifetime and quantum yield. These findings provide a useful roadmap for the development of highly performing purely organic solid-state emitters based on the persulfurated benzene platform., (© 2024 Wiley-VCH GmbH.)

Understanding the local triplet (3LE), charge transfer triplet (3CT), and charge transfer singlet (1CT) is of great importance in designing thermally activated delayed fluorescence (TADF) and room‐temperature phosphorescence (RTP) materials for their use in organic light‐emitting devices (OLEDs), sensing, and bioimaging. Herein, two phenothiazine–quinoline conjugates (PTzQ1, PTzQ2) in which the donor (PTz) and acceptor (Q1, Q2) parts are held in near‐orthogonal orientation that gives rise to spatial separation of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) are reported. Photophysical studies of both conjugates along with their individual components (PTz, Q1, Q2) show that TADF occurs via reverse intersystem crossing (rISC) from the upper‐level local triplet (3LE) to lower‐level singlet 1CT mediated by vibronic coupling between 3LE and 3CT, whereas RTP is realized from 3LE. It is found that all three excited states are close in energy, 0.16–0.19 eV (3LE−1CT), 0.02–0.03 eV (1CT−3CT), and 0.14–0.16 eV (3LE−3CT) with the order of 3LE > 1CT > 3CT. Both conjugates exhibit a high rate constant of rISC (krISC, 7.9–9.7 × 105 s−1), resulting in external quantum efficiency (EQE) values of ≈4.7% (solution processed) with emission from both RTP and TADF components.

Purely organic circularly polarized luminescent (CPL) materials have attracted much attention owing to their fascinating photophysical properties and potential applications in the fields of optical data storage, smart sensors/probers, high‐resolution 3D display, and so on. With the development of photophysical science, the emergence of some novel emission phenomena, such as thermally activated delayed fluorescence (TADF) and room‐temperature phosphorescence (RTP), have become hot topics and enriched CPL materials. However, there is no systematic review that summarizes the recent development of chiral small organic molecules (SOMs) with TADF and RTP characters. In this minireview, the progress of purely organic CPL materials in the last 5 years is reviewed by categorizing into chiral fluorescence molecules, chiral TADF molecules, and chiral RTP molecules. Furthermore, the design strategy of chiral TADF emitters is discussed and the correlation between chirality and RTP properties is concluded.

Herein, a type of light- and heat-driven flexible supramolecular polymer with reversibly long-lived phosphorescence and photochromism is constructed from acrylamide copolymers with 4-phenylpyridinium derivatives containing a cyano group (P-CN, P-oM, P-mM), sulfobutylether-β-cyclodextrin (SBCD), and polyvinyl alcohol (PVA). Compared to their parent solid polymers, these flexible supramolecules based on the non-covalent cross-linking of copolymers, SBCD, and PVA efficiently boost the phosphorescence lifetimes (723.0 ms for P-CN, 623.0 ms for P-oM, 945.8 ms for P-mM) through electrostatic interaction and hydrogen bonds. The phosphorescence intensity/lifetime, showing excellent responsiveness to light and heat, sharply decreased after irradiation with a 275 nm flashlight or sunlight and gradually recovered through heating. This is accompanied by the occurrence and fading of visible photochromism, manifesting as dark green for P-CN and pink for P-oM and P-mM. These reversible photochromism and phosphorescence behaviors are mainly attributed to the generation and disappearance of organic radicals in the 4-phenylpyridinium derivatives with a cyano group, which can guide tunable luminescence and photochromism., (© 2024 Wiley‐VCH GmbH.)

Organic semiconductors provide the potential of biodegradable technologies, but prototypes do only rarely exist. Transparent, ultrathin programmable luminescent tags (PLTs) are presented for minimalistic yet efficient information storage that are fully made from biodegradable or at least industrially compostable, ready-to-use materials (bioPLTs). As natural emitters, the quinoline alkaloids show sufficient room temperature phosphorescence when being embedded in polymer matrices with cinchonine exhibiting superior performance. Polylactic acid provides a solution for both the matrix material and the flexible substrate. Room temperature phosphorescence can be locally controlled by the oxygen concentration in the film by using Exceval as additional oxygen blocking layers. These bioPLTs exhibit all function-defining characteristics also found in their regular nonenvironmentally degradable analogs and, additionally, provide a simplified, high-contrast readout under continuous-wave illumination as a consequence of the unique luminescence properties of the natural emitter cinchonine. Limitations for flexible devices arise from limited thermal stability of the polylactic acid foil used as substrate allowing only for one writing cycle and preventing an annealing step during fabrication. Few-cycle reprogramming is possible when using the architecture of the bioPLTs on regular quartz substrates. This work realizes the versatile platform of PLTs with less harmful materials offering more sustainable use in future., (© 2024 The Authors. Advanced Materials published by Wiley‐VCH GmbH.)

Tunable-lifetime room-temperature phosphorescence (RTP) materials have been widely studied due to their broad applications. However, only few reports have achieved wide-range lifetime modulation. In this work, ultra-wide range tunable-lifetime efficient dark blue RTP materials were realized by doping methyl benzoate derivatives into polyvinyl alcohol (PVA) matrix. The phosphorescence lifetimes of the doped films can be increased from 32.8 ms to 1925.8 ms. Such wide range of phosphorescence lifetime modulation is extremely rare in current reports. Moreover, the phosphorescence emission of the methyl 4-hydroxybenzoate-doped film is located in the dark blue region and the phosphorescence quantum yield reaches as high as 15.4 %, which broadens their applications in organic optoelectronic information. Further studies demonstrated that the reason for the tunable lifetime was that the magnitude of the electron-donating ability of the substituent group modulates the HOMO-LUMO and singlet-triplet energy gap of methyl benzoate derivatives, as well as the ability to non-covalent interactions with PVA. Moreover, the potential applications of luminescent displays and optical anti-counterfeiting of these high-performance dark blue RTP materials have been conducted., (© 2024 Wiley-VCH GmbH.)

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., (© 2024 Wiley-VCH GmbH.)

Molecules with nonplanar architectures are highly desirable due to their unique topological structures and functions. We report here the synthesis of two molecular containers (1 ⋅ 3Br - and 1 ⋅ 3Cl - ), which utilize intramolecular cation-π interactions to enforce macrocylic arrangements and exhibit high binding affinity and luminescent properties. Remarkably, the geometry of the cation-π interaction can be flexibly tailored to achieve a precise ring arrangement, irrespective of the angle of the noncovalent bonds. Additionally, the C-H⋅⋅⋅Br - hydrogen bonds within the container are also conducive to stabilizing the bowl-shaped conformation. These bowl-shaped conformations were confirmed both in solution through NMR spectroscopy and in the solid state by X-ray studies. 1 ⋅ 3Br - shows high binding affinity and selectivity: F - >Cl - , through C-H⋅⋅⋅X - (X=F, Cl) hydrogen bonds. Additionally, these containers exhibited blue fluorescence in solution and yellow room-temperature phosphorescence (RTP) in the solid state. Our findings illustrate the utility of cation-π interactions in designing functional molecules., (© 2024 Wiley-VCH GmbH.)

Recently, there has been intense interest in pure organic room-temperature phosphorescence (ORTP) from cocrystals composed of 1,4-diiodotetrafluorobenzene (DITFB) and a variety of polycyclic aromatic hydrocarbons (PAHs) or their derivatives. To expand the possibility of halogen bonding-based cocrystals, the relationship between the crystal packing motifs and ORTP characteristics in binary cocrystals composed of DITFB and PAHs of phenanthrene (Phen), chrysene (Chry), and pyrene (Pyr), respectively, is investigated. The σ-hole···π and π-hole···π interactions determine not only the crystal packing motifs but also photoluminescence quantum yields (PLQYs). The Phen-DITFB and Chry-DITFB binary cocrystals with σ-hole···π interactions show higher PLQY compared with the Pyr-DITFB binary cocrystal with π-hole···π interaction. Further, to clarify the effect of crystal structures on PLQY, ternary cocrystals are prepared by partially doping Pyr into Phen-DITFB. The crystal packing motif of the ternary cocrystal originates from a Phen-DITFB cocrystal with σ-hole···π interaction, and some of the Phen sites are randomly replaced with Pyr molecules. The ORTP emission is derived from Pyr. The maximum PLQY is >20% due to suppressing nonradiative decay by changing the crystal packing motif., (© 2023 Wiley‐VCH GmbH.)

Organic room‐temperature phosphorescence (RTP) has attracted tremendous attention in recent years due to its potential utility in combination with artificial soft materials. Herein, a room‐temperature‐phosphorescent hybrid xerogel held together by electrostatic and host–guest interactions is reported. The xerogel is constructed by noncovalent complexation of 7‐[6‐deoxy‐6‐(2‐sulfonic)]‐β‐cyclodextrin (SCD) with the phosphor bromophenyl‐methyl‐pyridinium chloride (PYCl) and in situ incorporation of the anionic SCD⊃PYCl complex into a cationic amino clay (AC) via electrostatic interactions. The resulting xerogel, designated AC/SCD⊃PYCl, has a network structure that can suppress vibrational and nonradiative relaxation of the phosphor, leading to green RTP emission as well as good fluorescence–phosphorescence dual emission. Notably, the intensity of the xerogel RTP varies with humidity and can be switched on and off repeatedly, which indicates that the xerogel has potential utility as an organic light‐emitting humidity‐sensing material.

The development of a persistent luminescence system with long-lived phosphorescence and color-tunable afterglow at room temperature represents a challenge, largely due to the intensive non-radiative deactivation pathway. In this study, an ultralong-lived room temperature phosphorescence (RTP) system has been achieved using a hydrogen-bonding strategy where poly(vinyl alcohol) (PVA) matrices were doped with tryptophan (Trp) derivatives. The PVA film doped with N-α-(9-Fluorenylmethoxycarbonyl)-L-tryptophan (Fmoc-L-Trp) exhibited a long-lived phosphorescence emission of up to 3859.70 ms, and a blue afterglow for a duration greater than 34 s, under ambient conditions. The introduction of two other fluorescent dyes (i. e., Rhodamine B and Basicred14) to the PVA film facilitates adjustment to the color of the afterglow from blue to orange, and pink, by a triplet-to-singlet Förster-resonance energy transfer (TS-FRET) process. These films have been successfully applied in silk-screen printing and in multicolor afterglow light-emitting diode (LED) arrays., (© 2024 Wiley‐VCH GmbH.)

Metal-organic hybrid (MOH) materials with room-temperature phosphorescence (RTP) have drawn attention in recent years due to their superior RTP properties of high phosphorescence efficiency and ultralong emission lifetime. Great achievement has been realized in developing MOH materials with high-performance RTP, but a systematic study on MOH materials with RTP feature is lacking. This review highlights recent advances in metal-organic hybrid RTP materials. The molecular packing, the photophysical properties, and their applications of metal-organic hybrid RTP materials are discussed in detail. Metal-organic hybrid RTP materials can be divided into six parts: coordination polymers, metal-organic frameworks (MOFs), metal-halide hybrids, organic ionic crystals, organic ionic polymers, and organic-inorganic hybrid perovskites. These RTP materials have been successfully applied in time-resolved data encryption, fingerprint recognition, information logic gates, X-ray imaging, and photomemory. This review not only provides the basic principles of designing RTP metal-organic hybrids, but also propounds the future research prospects of RTP metal-organic hybrids. This review offers many effective strategies for developing metal-organic hybrids with excellent RTP properties, thus satisfying practical applications., (© 2024 Wiley‐VCH GmbH.)

Bright afterglow room-temperature phosphorescence (RTP) soon after ceasing excitation is a promising technique for greatly increasing anti-counterfeiting capabilities. The development of a process for rapid high-resolution afterglow patterning of crystalline materials can improve both high-speed fabrication of anti-counterfeiting afterglow media and stable afterglow readout compared with those achieved with amorphous materials. Here, the high-resolution afterglow patterning of crystalline materials via cooperative organic vapo- and photo-stimulation is reported. A single crystal of (S)-(-)-2,2'-bis(diphenylphosphino)-5,5',6,6',7,7'8,8'-octahydro-1,1'-binaphthyl [(S)-H 8 -BINAP] doped with (S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl [(S)-BINAP] shows green afterglow RTP. Crystals of (S)-BINAP-doped (S)-H 8 -BINAP changed to an amorphous state with no afterglow capability on weak continuous photoirradiation under dichloromethane (DCM) vapor. Photoirradiation induced oxidation of the (S)-H 8 -BINAP host molecule in the crystal. The oxidized (S)-H 8 -BINAP forms on the crystal surface strongly interacted with DCM molecules, which induces melting of the (S)-BINAP-doped (S)-H 8 -BINAP crystal and trigger formation of an amorphous state without an afterglow capability. High-resolution afterglow patterning of the crystalline film is rapidly achieved by using cooperative organic vapo- and photo-stimulation. In addition to the benefit of rapid afterglow patterning, the formed afterglow images of the crystalline film can be repeatedly read out under ambient conditions without DCM vapor., (© 2023 Wiley‐VCH GmbH.)

Carbonized polymer dots (CPDs) with a circularly polarized fluorescence property have received increasing attention in recent years. However, it is still a great challenge to construct circularly polarized room-temperature phosphorescence (CPRTP) CPDs. Herein, a simple approach to the synthesis of intrinsically CPRTP CPDs for the first time by utilizing sodium alginate and l-/d-arginine as precursors under relatively mild reaction conditions is presented. Notably, the CPDs exhibit both chirality and green RTP in solid states. Furthermore, color-tunable CPRTP is successfully achieved by engineering chiral light-harvesting systems based on circularly polarized phosphorescence resonance energy transfer (C-PRET) where the CPDs with green RTP function as an initiator of chirality and light absorbance, and commercially available fluorescent dyes with different emission colors ranging from yellow to red serve as the terminal acceptors. Through one-step or sequential C-PRET, the light-harvesting systems can simultaneously furnish energy transfer and chirality transmission/amplification. Given the multicolor long afterglow, lifetime-tunable, and CPRTP properties, their potential applications in multiple information encryption are demonstrated., (© 2023 Wiley‐VCH GmbH.)

Achieving efficient near-infrared room-temperature phosphorescence of purely organic phosphors remains scarce and challenging due to strong nonradiative decay. Additionally, the investigation of triplet excimer phosphorescence is rarely reported, despite the fact that excimer, a special emitter commonly formed in crystals with strong π-π interactions, can efficiently change the fluorescent properties of compounds. Herein, a series of dithienopyrrole derivatives with low triplet energy levels and stable triplet states, exhibiting persistent near-infrared room-temperature phosphorescence, is developed. Via the modification of halogen atoms, the crystals display tunable emissions of monomers from 645 to 702 nm, with a maximum lifetime of 3.68 ms under ambient conditions. Notably, excimer phosphorescence can be switched on at low temperatures, enabled by noncovalent interactions rigidifying the matrix and stabilizing triplet excimer. Unprecedentedly, the dynamic transition process is captured between the monomer and excimer phosphorescence with temperature variations, revealing that the unstable triplet excimers in crystals with a tendency to dissociate can result in the effective quench of room-temperature phosphorescence. Excited state transitions across varying environments are elucidated, interpreting the structural dynamics of the triplet excimer and demonstrating strategies for devising novel near-infrared phosphors., (© 2024 Wiley‐VCH GmbH.)

Tautomers coexisting in an equilibrium system have significant potential for regulating luminescent properties because of their structural differences. However, separating and stabilizing tautomers at room temperature is a considerable challenge. In this study, it is found that hydrogen-bonded organic frameworks (HOFs) composed of Br - anions can effectively separate and stabilize two proton-transfer tautomers of triarylformamidinium bromide: namely, the nitrogen cation (BA-N) and carbon cation (BA-C). The BA-N crystal consisting of a dense anionic HOF and parallelly aligned organic cations exhibits green thermally activated delayed fluorescence and red room-temperature phosphorescence (RTP). The BA-C crystal contains acetone molecules that induce an antiparallel arrangement of the organic cations to form a loose HOF, producing blue prompt fluorescence and green RTP. Interestingly, switching of the HOFs between BA-N and BA-C can be achieved through the uptake and release of acetone, thereby dynamically adjusting multiple luminescent properties. Consequently, the HOF crystals can be used for the highly sensitive and specific sensing of acetone with a detection limit of 66.74 ppm. This study not only stabilizes tautomeric luminescent materials at room temperature, but also provides a new method for constructing smart HOFs with a sensitive response to a stimulus., (© 2024 Wiley-VCH GmbH.)

Purely organic materials exhibiting room temperature phosphorescence (RTP) are promising candidates for oxygen sensors and information encryption owing to their cost-effective and environmentally friendly nature. Herein, we report a bimolecular RTP system where DTBU acts as the guest and TBBU serves as the host. In contrast to previously reported results, we find that both pure DTBU and TBBU do not exhibit RTP in the solid state even under N 2 atmosphere. A DTBU/TBBU system with a low doping ratio (0.1 mol %) exhibits persistent yellowish-green afterglow with a lifetime of 340 ms and is highly sensitive to oxygen. A DTBU/TBBU system with a higher doping ratio (10 mol %) maintains a phosphorescence lifetime of 179 ms under air. Applications of DTBU/TBBU at varied doping ratios in both oxygen sensing and information encryption are demonstrated. We propose that the T 1 state of TBBU acts as an energy transfer intermediate between T n and T 1 of DTBU, ultimately leading to the generation of persistent RTP. Overall, this work demonstrates the critical importance of material purity in the design of RTP systems, and how an understanding of host-guest doping enables their photophysical properties to be precisely tuned., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Achieving circularly polarized organic ultralong room-temperature phosphorescence (CP-OURTP) with a high luminescent dissymmetry factor (g lum ) is crucial for diverse optoelectronic applications. In particular, dynamically controlling the dissymmetry factor of CP-OURTP can profoundly advance these applications, but it is still unprecedented. This study introduces an effective strategy to achieve photoirradiation-driven chirality regulation in a bilayered structure film, which consists of a layer of soft helical superstructure incorporated with a light-driven molecular motor and a layer of room-temperature phosphorescent (RTP) polymer. The prepared bilayered film exhibits CP-OURTP with an emission lifetime of 805 ms and a g lum value up to 1.38. Remarkably, the g lum value of the resulting CP-OURTP film can be reversibly controlled between 0.6 and 1.38 over 20 cycles by light irradiation, representing the first example of dynamically controlling the g lum in CP-OURTP., (© 2024 Wiley-VCH GmbH.)

Organic materials with room-temperature phosphorescence (RTP) are in high demand for optoelectronics and bioelectronics. Developing RTP materials highly relies on expert experience and costly excited-state calculations. It is a challenge to find a tool for effectively screening RTP materials. Herein we first establish ground-state orbital descriptors (π FMOs ) derived from the π-electron component of the frontier molecular orbitals to characterize the RTP lifetime (τ p ), achieving a balance in screening efficiency and accuracy. Using the π FMOs , a data-driven machine learning model gains a high accuracy in classifying long τ p , filtering out 836 candidates with long-lived RTP from a virtual library of 19,295 molecules. With the aid of the excited-state calculations, 287 compounds are predicted with high RTP efficiency. Impressively, experiments further confirm the reliability of this workflow, opening a novel avenue for designing high-performance RTP materials for potential applications., (© 2023 Wiley-VCH GmbH.)

The accurate thermosensing requires a minimum impact of autofluorescence and light scattering from the samples. In this study, we discovered that commercially available benzene-1,4-diboronic acid (BDBA) doped co-crystals with trimethylolpropane (TMP) exhibit excellent thermochromic dual phosphorescence properties over a wide temperature range from -132 to 40 °C, despite its simple structure that does not have any donor-acceptor linkage. The dual phosphorescence was consisted of monomeric benzene-1,4-diboronate (BDBA ester) and aggregation-stabilized species. With an increase in temperature, the emission intensity from the monomeric state significantly decreased, whereas that originating from the aggregated state remained almost constant owing to the difference in their thermal stabilities. Further investigation revealed that molecular distortions in singlet excited states enable efficient intersystem crossing, causing efficient phosphorescence from the monomeric state of BDBA ester., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Boosting the circularly polarized luminescence of small organic molecules has been a stubborn challenge because of weak structure rigidity and dynamic molecular motions. To investigate and eliminate these factors, here, we carried out the structure-property relationship studies on a newly-developed axial chiral scaffold of bidibenzo[b,d]furan. The molecular rigidity was finely tuned by gradually reducing the alkyl-chain length. The environmental factors were considered in solution, crystal, and polymer matrix at different temperatures. As a result, a significant amplification of the dissymmetry factor g lum from 10 -4 to 10 -1 was achieved, corresponding to the situation from (R)-4C in solution to (R)-1C in polymer film at room temperature. A synergistic strategy of increasing the intramolecular rigidity and enhancing the intermolecular interaction to restrict the molecular motions was thus proposed to improve circularly polarized luminescence. The though-out demonstrated relationship will be of great importance for the development of high-performance small organic chiroptical systems in the future., (© 2023 Wiley-VCH GmbH.)

Luminescent metal clusters have attracted great interest in current research; however, the design synthesis of Al clusters with color-tunable luminescence remains challenging. Herein, an [Al 8 (OH) 8 (NA) 16 ] (Al 8 , HNA = nicotinic acid) molecular cluster with dual luminescence properties of fluorescence and room-temperature phosphorescence (RTP) is synthesized by choosing HNA ligand as phosphor. Its prompt photoluminescence (PL) spectrum exhibits approximately white light emission at room temperature. Considering that halogen atoms can be used to regulate the RTP property by balancing the singlet and triplet excitons, different CdX 2 (X - = Cl - , Br - , I - ) are introduced into the reactive system of the Al 8 cluster, and three new Al 8 cluster-based metal-organic frameworks, {[Al 8 Cd 3 Cl 5 (OH) 8 (NA) 17 H 2 O]·2HNA} n (CdCl 2 -Al 8 ), {[Al 8 Cd 4 Br 7 (OH) 8 (NA) 16 CH 3 CN]·NA·HNA} n (CdBr 2 -Al 8 ) and {[Al 8 Cd 8 I 16 (OH) 8 (NA) 16 ]} n (CdI 2 -Al 8 ) are successfully obtained. They realize the color tunability from blue to yellow at room temperature. The origination of fluorescence and phosphorescence has also been illustrated by structure-property analysis and theoretical calculation. This work provides new insights into the design of multicolor luminescent metal cluster-based materials and develops advanced photo-functional materials for multicolor display, anti-counterfeiting, and encryption applications., (© 2023 Wiley-VCH GmbH.)

Long-lived room-temperature phosphorescence (RTP) of organic materials holds a significant potential for optical information. Circularly polarized organic ultralong room-temperature phosphorescence (CP-OURTP) with extremely high dissymmetry factor (g lum ) values is even highly demanded and considerably challenging. Here, an effective strategy is introduced to realize CP-OURTP with an emission decay time of 735 ms and a g lum value up to 1.49, which exceeds two orders of magnitude larger than previous records, through a system composed of RTP polymers and chiral helical superstructures. The system exhibits excellent stability under multiple cycles of photoirradiation and thermal treatment, and is further employed for information encryption based on optical multiplexing. The results are anticipated to lay the foundation for the development of CP-OURTP materials in advanced photonic applications., (© 2023 Wiley-VCH GmbH.)

Construction of new system and exploration of new approach are of great importance for the improvement of their photophysical properties to meet the growing various uses of phosphorescent materials. Triphenylmethane (TPM), composed only of carbon and hydrogen, exhibits excellent color tunable phosphorescence in air, with ultralong lifetime (836 ms), and wide color-tunable range (from cyan to green, then to yellow and finally to orange, 525 nm-616 nm). Through careful comparison with the single crystal diffraction structure of tetraphenylmethane (TTPM) and theoretical calculation analysis, we believe that various clusters formed through space interactions are crucial for color-tunable phosphorescence., (© 2023 Wiley-VCH GmbH.)

The development of organic materials that deliver room-temperature phosphorescence (RTP) is highly interesting for potential applications such as anticounterfeiting, optoelectronic devices, and bioimaging. Herein, a molecular chaperone strategy for controlling isolated chromophores to achieve high-performance RTP is demonstrated. Systematic experiments coupled with theoretical evidence reveal that the host plays a similar role as a molecular chaperone that anchors the chromophores for limited nonradiative decay and directs the proper conformation of guests for enhanced intersystem crossing through noncovalent interactions. For deduction of structure-property relationships, various structure-related descriptors that correlate with the RTP performance are identified, thus offering the possibility to quantitatively design and predict the phosphorescent behaviors of these systems. Furthermore, application in thermal printing is well realized for these RTP materials. The present work discloses an effective strategy for efficient construction of organic RTP materials, delivering a modular model which is expected to help expand the diversity of desirable RTP systems., (© 2023 Wiley-VCH GmbH.)

A rational molecular design strategy facilitates the development of a purely organic room-temperature phosphorescence (RTP) material system with precisely regulated luminescence properties, which surely promotes its functional integration and intelligent application. Here, a functional unit combination strategy is proposed to design novel RTP molecules combining a folding unit with diverse luminescent cores. The different luminescent cores are mainly responsible for tunable RTP properties, while the folding unit contributes to the spin-orbit coupling (SOC) enhancement, which makes the RTP material design as workable as the building block principle. By this strategy, a series of color/lifetime-tunable RTP materials is achieved with unique photo-responsive RTP enhancement when subjected to UV irradiation, which expands their application scenarios in reusable privacy tags, advanced "4D" encryption, and phase separation analysis of blended polymers. This work suggests a simple and effective strategy to design purely organic RTP materials with tunable color and lifetime, and also provides new application options for photo-responsive dynamic RTP materials., (© 2023 Wiley-VCH GmbH.)

Silicon nanocrystals (SiNCs) have attracted extensive attention in many advanced applications due to silicon's high natural abundance, low toxicity, and impressive optical properties. However, these applications are mainly focused on fluorescent SiNCs, little attention is paid to SiNCs with room-temperature phosphorescence (RTP) and their relative applications, especially water-dispersed ones. Herein, this work presents water-dispersible RTP SiNCs (UA-SiNCs) and their optical applications. The UA-SiNCs with a uniform particle size of 2.8 nm are prepared by thermal hydrosilylation between hydrogen-terminated SiNCs (H-SiNCs) and 10-undecenoic acid (UA). Interestingly, the resultant UA-SiNCs can exhibit tunable long-lived RTP with an average lifetime of 0.85 s. The RTP feature of the UA-SiNCs is confirmed to the n-π* transitions of their surface C═O groups. Subsequently, new dual-modal emissive UA-SiNCs-based ink is fabricated by blending with sodium alginate (SA) as the binder. The customized anticounterfeiting labels are also prepared on cellulosic substrates by screen-printing technique. As expected, UA-SiNCs/SA ink exhibits excellent practicability in anticounterfeiting applications. These findings will trigger the rapid development of RTP SiNCs, envisioning enormous potential in future advanced applications such as high-level anti-counterfeiting, information encryption, and so forth., (© 2023 Wiley-VCH GmbH.)

Achieving aqueous solution enhanced room temperature phosphorescence (RTP) is critical for the applications of RTP materials in solution phase, but which faces a great challenge. Herein, for the first time, a strategy of coordination-induced structural rigidity is proposed to achieve enhanced quantum efficiency of aluminum/scandium-doped phosphorescent microcubes (Al/Sc-PMCs) in aqueous solution. The Al/Sc-PMCs in a dry state exhibit a nearly invisible blue RTP. However, they emit a strong RTP emission in aqueous solution with a RTP intensity increase of up to 22.16-times, which is opposite to common solution-quenched RTP. The RTP enhancement mechanism is attributed to the abundant metal sites (Al 3+ and Sc 3+ ions) on the Al/Sc-PMCs surface that can tightly combine with water molecules through the strong coordination. Subsequently, these coordinated water molecules as the bridging agent can bind with surface groups by hydrogen bonding interaction, thereby rigidifying chemical groups and inhibiting their motions, resulting in the transition from the nonradiative decay to the radiative decay, which greatly enhances the RTP efficiency of the Al/Sc-PMCs. This work not only develops a coordination rigidity strategy to enhance RTP intensity in aqueous solution, but also constructs a phosphorescent probe to achieve reliable and accurate determination of analyte in complex biological matrices., (© 2023 Wiley-VCH GmbH.)

The development of flexible, room-temperature phosphorescence (RTP) materials remains challenging owing to the quenching of their unstable triplet excitons via molecular motion. Therefore, a polymer matrix with T g higher than room temperature is required to prevent polymer segment movement. In this study, a RTP material was developed by incorporating a 4-biphenylboronic acid (BPBA) phosphor into a poly(vinylidene fluoride) (PVDF) matrix (T g =-27.1 °C), which exhibits a remarkable UV-light-dependent oxygen consumption phosphorescence with a lifetime of 1275.7 ms. The adjustable RTP performance is influenced by the crystallinity and polymorph (α, β, and γ phases) fraction of PVDF, therefore, the low T g of the PVDF matrix enables the polymeric segmental motion upon microwave irradiation. Consequently, a reduction in the crystallinity and an increase in the α phase fraction in PVDF film induces RTP after 2.45 GHz microwave irradiation. These findings open up new avenues for constructing crystalline and phase-dependent RTP materials while demonstrating a promising approach toward microwave detection., (© 2023 Wiley-VCH GmbH.)

Afterglow room-temperature emission that is independent of autofluorescence after ceasing excitation is a promising technology for state-of-the-art bioimaging and security devices. However, the low brightness of the afterglow emission is a current limitation for using such materials in a variety of applications. Herein, the continuous formation of condensed triplet excitons for brighter afterglow room-temperature phosphorescence is reported. (S)-(-)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl ((S)-BINAP) incorporated in a crystalline host lattice showed bright green afterglow room-temperature phosphorescence under strong excitation. The small triplet-triplet absorption cross-section of (S)-BINAP in the whole range of visible wavelengths greatly suppressed the deactivation caused by Förster resonance energy transfer from excited states of (S)-BINAP to the accumulated triplet excitons of (S)-BINAP under strong continuous excitation. The steady-state concentration of the triplet excitons for (S)-BINAP reached 2.3 × 10 -2  M, producing a bright afterglow. Owing to the brighter afterglow, afterglow detection using individual particles with sizes approaching the diffraction limit in aqueous conditions and irradiance-dependent anticounterfeiting can be achieved., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Circularly polarized luminescence (CPL) materials with clustering-triggered emission (CTE) characteristic have gradually attracted attention for their unique photophysical properties. However, the majority of reported clusteroluminogens lack chirality and exhibit heterogeneity, making it challenging to achieve a well-defined helical structure necessary for efficient CPL with high dissymmetry factor (g lum ). In this paper, chiral liquid crystals are constructed to obtain CTE-based CPL materials with high g lum values. Side chain liquid crystal polymer PM6Chol bearing cholesterol clusteroluminogens are designed and synthesized. PM6Chol-coated film and PM6Chol thermal-treated film are also successfully prepared by different film-forming methods. Both the films inherit the CTE characteristic of cholesterol and show excitation wavelength-dependent luminescent behavior. However, the two polymer films exhibit different liquid crystal phase structures, with PM6Chol-coated film being a chiral bilayer smectic C phase and PM6Chol thermal-treated film being an achiral bilayer smectic A phase. Attributed to helical arrangement of cholesterol, PM6Chol-coated film emits efficient CPL with g lum values up to 1.0 × 10 -1 . For PM6Chol thermal-treated film, no CPL signal is detected due to the absence of helical structure. However, it shows obvious room-temperature phosphorescence with 2.0 s afterglow and 23.9 ms lifetime., (© 2023 Wiley-VCH GmbH.)

Chiral nematic liquid crystals (N*-LCs) can tremendously amplify circularly polarized luminescence (CPL) signals. Doped emissive N*-LCs have been substantially explored. However, their CPL performances still need to be improved, mainly due to the unsatisfying helical twisting power (HTP) of commonly used chiral fluorescent dopants. Chiral fluorescent helical polymers (CFHPs) have outstanding optical activity and CPL performance. The present contribution reports the first success in constructing emissive N*-LCs by doping CFHP into nematic liquid crystals (5CB, N-LCs). The helical assembly structures of N*-LCs effectively amplify the CPL signals of the CFHP. Owing to the high HTP of CFHP, the selective reflection band of N*-LC can be adjusted to fully cover its emission band. A nearly pure CPL with a dissymmetry factor (g lum ) up to -1.87 is realized at 9 wt% doping concentration. Taking advantage of the selective reflection mechanism, multi-color CPL-active N*-LCs with high g lum are fabricated via further adding achiral fluorophores. Also noticeably, circularly polarized room-temperature phosphorescence with g lum up to -1.57 is achieved. Anti-counterfeiting application is demonstrated by exploiting multi-mode optical characteristics of the created N*-LCs. The established strategy for constructing emissive N*-LCs provides a platform for future exploring of CPL-active N*-LCs., (© 2023 Wiley-VCH GmbH.)

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., (© 2023 Wiley-VCH GmbH.)

Smart-response materials with ultralong room-temperature phosphorescence (RTP) are highly desirable, but they have rarely been described, especially those originating from sustainable polymers. Herein, a variety of cellulose derivatives with 1,4-dihydropyridine (DHP) rings are synthesized through the Hantzsch reaction, giving impressive RTP with a long lifetime of up to 1251 ms. Specifically, the introduction of acetoacetyl groups and DHP rings promotes the spin-orbit coupling and intersystem crossing process; and multiple interactions between cellulose induce clustering and inhibit the nonradiative transitions, boosting long-live RTP. Furthermore, the resulting transparent and flexible cellulose films also exhibit excitation-dependent and color-tunable afterglows by introducing different extended aromatic groups. More interestingly, the RTP performance of these films is sensitive to water and can be repeated in response to wet/dry stimuli. Inspired by these advantages, the RTP cellulose demonstrates advanced applications in information encryption and anti-counterfeiting. This work not only enriches the photophysical properties of cellulose but also provides a versatile platform for the development of sustainable afterglows., (© 2023 Wiley-VCH GmbH.)