A strategy to activate room-temperature phosphorescence (RTP) of coumarin derivatives was reported. The rigid environment and efficient energy transfer resulted in an outstanding RTP emission, enabling advanced applications in information encryption.

We propose a strategy in which polar guest molecules induce through-space conjugation to enhance the room-temperature phosphorescence performance of a host matrix in a host-guest doping system. By incorporating polar coumarin derivatives into aromatic carboxylic acid, strong intermolecular interactions were established via through-space conjugation, leading to a significant extension of the phosphorescence lifetime.

Inorganic-organic hybridization has emerged as an effective approach to activate organic room-temperature phosphorescence (RTP), yet the underlying luminescence mechanisms remain somewhat ambiguous. In this study, we have developed a novel inorganic-organic hybridization system with long-life RTP by choosing coumarin derivatives with donor–π–receptor (D–π–A) structures (7-HMCum, 7-DEAMCum and 7-AMCum) as the organic guests and heated boric acid (HBA, rigid boron oxide) as the inorganic matrix. By altering the substituents at 7-position of the coumarin guests, blue and green afterglow were obtained. Among them, 7-HMCum @ HBA demonstrated outstanding phosphorescent properties, with a phosphorescence lifetime of 2.88 s, a phosphorescence quantum yield of 19.36 % and afterglow duration of 24 s. Based on their photophysical investigation, molecular geometries and chemical bonding between the host and the guest in the ground state (O→B coordinate bond) and excited state (O–B covalent bond), as well as EPR measurement, dual-channel parallel luminescence mechanism was proposed. One is charge separation-long-range charge transfer-charge recombination luminescent channel in the case of the guest is photoirradiated; the other one involves Dexter energy transfer channel in the case of the host is photoirradiated. Dual-Channel can work synergistically. Based on the long afterglow time and adjustable colors of the doped materials, application in the fields of information anti-counterfeiting and digital encryption has been demonstrated.

Purely organic blue room‐temperature phosphorescent materials are scarce. In this work, ten blue RTP film materials are designed and synthesized by doping electron‐deficient benzene derivatives into poly(acrylic acid) (PAA). Noteworthy, the phosphorescence performance of the simple benzenes doped in PAA is superior to that in polyvinyl alcohol (PVA). The phosphorescence lifetime of 4‐cyanobenzoic acid methyl ester@PAA reaches up to 1486.2 ms. A high phosphorescence quantum efficiency of 23.3% is achieved in dimethyl terephthalate@PAA film. Theoretical calculations indicate that excellent phosphorescence performance is attributed to stronger electrostatic interactions between guests and PAA. Finally, the applications of the phosphorescent films in anti‐counterfeiting are demonstrated by inkjet printing and embroidering.

Room-temperature phosphorescence (RTP) materials hold promise for applications in bioimaging, anticounterfeiting, and optoelectronics, yet the design of purely organic RTP materials remains challenging due to significant non-radiative deactivation pathways. This study demonstrates a hydrogen-bonding strategy to suppress non-radiative transitions. Photophysical characterizations revealed that CCA/PAA exhibits green afterglow with a lifetime of 374 ms, while the BrCCA/PAA film achieved an enhanced quantum yield of 27.88 % due to the heavy-atom effect of the bromine. Further, by incorporating fluorescent dyes into CCA/PAA, multicolor Superfluorescence was achieved through triplet-to-singlet resonance energy transfer. These findings demonstrated the capability to tune afterglow colors and lifetimes by varying the doping ratios and energy acceptor types. This work not only provides insights into the role of hydrogen bonding and heavy-atom effects in RTP materials but also offers a pathway for designing advanced optical materials with tunable and high-performance characteristics.

Stimuli-responsive room-temperature phosphorescence (RTP) materials face challenges in environmental robustness and spatiotemporal controllability, particularly for oxygen- and temperature-sensitive applications. Here, by taking advantage of the high oxygen-permeability barrier of polyvinyl alcohol (PVA) and its photochemical reaction toward certain polyaromatic hydrocarbons, we present phenanthrene- and triphenylene-doped PVA films that exhibit photoactivatable and persistent RTP, with an observable afterglow time >70 s by the naked eye, likely via a kinetically trapped radical pathway. Specifically, such UV-enhanced persistent RTP occurs under both aerobic and anaerobic conditions, contrasting with a regular RTP turn-on mechanism via photo-induced molecular oxygen depletion. The activated RTP state shows temperature-dependent kinetic persistence, i.e., lasting ∼5 h at 25°C vs. ∼72 h at 4°C, creating irreversible RTP switching from “on” to “off” ideal for cumulative temperature monitoring. The PVA-based ink patterns printed on perishables (e.g., fresh milk bottles) can be used to quantify ambient exposure via RTP decay kinetics (relative intensity loss >84.2

In this study, we have proposed a protonic acid doping strategy to modulate the phosphorescence color of an organic/polymer host-guest doping system. Specifically, 1-naphthylamine(1-AN) doped in a poly(vinyl alcohol) (PVA) host exhibits yellow phosphorescence, while exhibiting green phosphorescence in poly(acrylic acid) (PAA, functions as both a matrix and a protonic acid, self-doping). The addition of hydrochloric acid into the 1-AN@PVA system also induces a green phosphorescence (external doping). This work provides an efficient approach for phosphorescence color tuning via acid doping.

A series of spirofluorene-triarylborane derivatives bearing tunable triarylamine donors (-H, -OMe, -SMe) were designed and synthesized to systematically investigate substituent effects on their photophysical behaviors. The methoxy-substituted compound FXylB-DOBPDA exhibits efficient thermally activated delayed fluorescence (TADF), characterized by a small singlet-triplet energy gap (ΔEST) of 0.05 eV, along with notable aggregation-induced emission enhancement (AIEE). Remarkably, through a host-guest doping strategy using triphenylamine (TPA) as the matrix, the system displays clearly visible afterglow under ambient conditions. In particular, the FXylB-DOBPDA@TPA codoped system achieves TADF-promoted long afterglow with lifetimes exceeding 100 ms. Additionally, reversible mechanochromic luminescence is observed, indicating multistimuli-responsive behavior. The combination of experimental analyses and theoretical calculations reveals that subtle changes in substituents critically influence intramolecular charge transfer and excited-state dynamics. These results offer valuable insights into molecular design strategies for achieving tunable emission in solid-state materials. With their integrated TADF, afterglow, and stimuli-responsive properties, these multifunctional materials demonstrate significant potential for applications in organic light-emitting diodes (OLEDs), mechanical sensors, anticounterfeiting labels, and optical storage technologies.

Doping guest materials into host materials with a confined space to suppress nonradiative decay is an effective strategy for achieving room-temperature phosphorescence (RTP). However, constructing host-guest doped materials with ultralong RTP (URTP) is still challenging. Herein, by embedding three coumarin derivatives into boric acid via one-step heat treatment, the URTP material with an afterglow lasting up to 60 s, a phosphorescence lifetime of 1.59 s, and a quantum yield of 18.14% was successfully prepared. Experimental results show that the dense 3D boron oxide network formed after heat treatment, along with the B-O covalent bonds and O→B coordination bonds between the host and guest, effectively suppresses nonradiative transitions through both physical and chemical confinement. More importantly, the oxygen vacancy defects formed in the doped material during heat treatment, combined with the charge-separated states generated in the guest molecules upon irradiation, together facilitated the long-range charge migration process. In addition, the charge recombination is accompanied by long-lived phosphorescence emission. Finally, the prepared URTP materials exhibit potential applications in the encryption and decryption of information in security fields.

An ambient-light-promoted stereospecific olefinic C(sp2)-S bond construction of thioacids and 1,1-diarylethenes has been demonstrated, affording various (Z)-vinyl thioesters in 51-85% yields under solvent- and catalyst-free conditions. Mechanistic studies indicated that the formation of thioacid-olefin complexes is responsible for generating a carbonyl thiyl radical and dioxygen in the air participates in the reaction and functions as a traceless reagent. Moreover, synthetic applications have been demonstrated by the gram scale synthesis and aggregation-induced emission property of representative compound 3i.

Yellow phosphorescence emission of 1,8-naphthalimide guest was activated by doping it into m-bromobenzaldehyde host (energy transfer mechanism). With the aim of alleviating the triplet-triplet annihilation of the benzaldehyde itself, m-dibromobenzene was introduced as the third component. As a result, the phosphorescence quantum yields of the doped crystallized materials significantly increase from 1.72 % for NI@mBA to 19.17 % for NI@mBA@mDBB (with 11 times enhancement) due to the cascade activation in the three-component system. The encryption/decryption using these phosphorescent doped materials provides potential application in security field. This study not only expands the scope of organic host molecules capable of activating the phosphorescence properties of NI, but also provides a platform for developing multi-component organic doping systems that can effectively regulate phosphorescence properties.

Achieving supercapacitors with high-performance operation in a low temperature environment is still a great challenge. Herein, an effective strategy that involves carbon cloth in situ grown 2D conductive dithiolene cobalt/nickel 2,3,6,7,10,11-triphenylenehexathiolate was developed to prepare hierarchical porous electrode materials (HTTP-M(Co/Ni)-CC). Without any conductive additive and binders, the specific capacitance values of HTTP-Co-CC and HTTP-Ni-CC reached up to 83.5 and 103.9 F g-1 at 10 mV s-1, respectively, when working at -60 degrees C. Compared with room-temperature capacitance values, the capacitance retention of HTTP-Co-CC and HTTP-Ni-CC remain 82.7% and 87.1%, respectively, which presents HTTP-Co-CC and HTTP-Ni-CC as unprecedented MOF electrode materials for use in the field of low-temperature energy storage. The outstanding performance at lower temperature can be attributed to an increased conductivity with decreasing temperature, hierarchical pore structures that facilitate the mass transfer of incompletely desolvated electrolyte ions at the interface and a flexible porous carbon cloth substrate that provides buffer space for volume expansion. This study not only demonstrates conductive dithiolene MOF-based electrodes for low-temperature high-performance energy storage, but also provides a promising prospect for the development of robust MOFs as a new family of active materials for supercapacitors operated under low-temperature environments. Two hierarchical porous conductive MOF-based electrodes show high capacitance retention when working at -60 degrees C. This represents an unprecedented MOF electrode material used in the field of low-temperature energy storage.

Multi-component doping has become an effective way to achieve efficient room-temperature phosphorescence. In this paper, green phosphorescence emission from coumarin derivatives, i.e., coumarin-3-carboxylic acid (CCA) and coumarin-3-carboxylic ester (CEt) are activated by doping them into polyvinyl alcohol (PVA) matrix (two component doping). Then, a series of metal salts (Ca2+, Al3+, Mn2+, and Zn2+) are added as the third component to construct three-component doping system, with the aim to further improve the phosphorescence properties of the polymer films. Among them, CaCl2 can significantly increase the emission intensity (9.2 times), prolong the phosphorescence lifetime (up to 361 ms), and increase the phosphorescence quantum yield (from 1.02% to 9.19%). The results indicated that RTP emission can be activated by inhibiting the non-radiative transition of coumarin derivatives embedded in the rigid PVA matrix. RTP performance can be further enhanced relying on the coordination effect between the coumarin guests and the metal salts. This study provides a simple and effective three-component doping method for boosting polymer film-based phosphorescence performance.

Dynamic room-temperature phosphorescence (DRTP) possesses a wide variety of advantages for developing smart optical devices to satisfy specific demands. In particular, the development of time-dependent phosphorescence colors (TDPC) towards anti-Kasha emission is challenging and less reported. Herein, a flexible multi-component film with controllably regulated lifetime/efficiency and TDPC was fabricated by encapsulating (4-([2,2 ':6 ',2 ''-terpyridin]-4 '-yl)phenyl)boronic acid (TPy-BA) and ZnCl2 into an amorphous poly(vinyl alcohol) (PVA) matrix. The coordination effects can promote ISC and restrict molecular motion. Significant improvements in phosphorescent lifetimes (from 99.13 ms to 218.75 ms) and efficiencies (from 3.90% to 6.51%) were achieved. Moreover, the triplet charge-transfer phophorescence was achieved in the TPy-BA/ZnI2/PVA-doped film. The afterglow color was also changed to green. Specially, the TDPC phenomenon from blue to green for the TPy-BA/ZnCl2/PVA films was observed at different delay times, which was the result of the emission from the anti-Kasha T2 energy level with a short lifetime (72.56 ms) and T1 emission with a long lifetime (218.75 ms), simultaneously. Based on these findings, the four-component TPy-BA/ZnCl2/NaI/PVA films were prepared, showing blue-shifted phosphorescence emission through gradually doping NaI. This phenomenon can be explained by the stronger coupling of the high-lying energy level towards external heavy atoms, facilitating the anti-Kasha emission from the T2 energy level. These flexible films have exhibited versatile applications in multi-level encryption, silk-screen printing, and high-definition displays. The time-dependent phosphorescence colors (TDPC) towards anti-Kasha emission from the T2 energy level was activated by coordination effects in the multi-component system TPy-BA/ZnCl2/PVA.

In the doped phosphorescent films, highly polar PAA afforded the best phosphorescence performance mainly due to the strong host–guest polar–polar interaction.

The unique properties of difluorinated compounds have attracted widespread attention in the fields of medicine and material sciences.The conversion of inexpensive and easily available trifluoromethyl groups into difluoro groups is of great importance in organic synthesis.However,there still exist great challenges in the selective cleavage of C—F bonds,because the dissociation energy of single C—F bond in trifluoromethyl group is much higher thanthat of the C—F bond in the difluoro unit of the generated product.Thus,the selective cleavage of C—F bond is difficult to control,which can easily lead to exces-sive defluorination.Compared with the traditional thermal reaction,the visible-light irradiated reaction provides an alternative pathway to achieve C—F cleavage more efficiently and selectively.The research progress on the selective cleavage of C—F bonds mediated by visible light in the past three years is summarized and its futureperspective is prospected.

The intermolecular interactions between small molecules and the matrix in a highly polar environment could easily lead to non-radiative transitions, which significantly hampers the development of high-performance persistent room-temperature phosphorescence (pRTP) materials in such condition. Herein, we introduce a novel strategy that integrates consecutive proton transfer and photo-induced charge transfer to facilitate triplet charge transfer emission in highly polar polymer matrix. In particular, doping aza-arene guests including 1,10phenanthroline (1,10-Phen), 2,9-dimethyl-1,10-phenanthroline (DM-Phen), and 7,8-benzoquinoline (7,8-BQ) into polyacrylic acid (PAA) resulted in superior pRTP properties compared to other polymer hosts. Spectroscopic investigations and theoretical calculations elucidate that this is attributed to the proton transfer and triplet charge transfer characteristics between the host and guest. Moreover, due to the rigid environment and space confinement provided by PAA, pRTP with the lifetime up to 841 ms is achieved. Capitalizing on the excellent water solubility of the doped PAA films, the inkjet printings have been executed, and showcasing the promising the potential applications of these pRTP materials in the field of information encryption.

Metal-organic frameworks (MOFs) have attracted significant attention as sorbents for gas separation and purification. Ideally, an industrially potential adsorbent should combine exceptional gas uptake, excellent stability, and a lower regeneration energy; however, it remains a great challenge. Here, by utilizing the pore space partition (PSP) strategy, we develop three isostructural MOF materials (Co-BDC-TPB, Co-DCBDC-TPB, and Co-DOBDC-TPB) based on pristine MIL-88(Co). The three pore-space-partitioned crystalline microporous MOFs have triangular bipyramid cages and segmented one-dimensional channels, and among them, Co-DOBDC-TPB exhibits the highest CO2 uptake capacity (4.35 mmol g-1) and good CO2/N2 (29.7) and CO2/CH4 (6.2) selectivity. The selectivity-capacity synergy endows it with excellent CO2/N2 and CO2/CH4 separation performance. Moreover, Co-DOBDC-TPB can complete desorption within 10 min. The satisfactory CO2 adsorption ability can be attributed to both microporous aperture arising from PSP and modification of the pore surface by the polar hydroxy group, which enhances the interaction between Co-DOBDC-TPB and CO2 molecules significantly. The exceptional regeneration property may be due to its lower CO2 isosteric heat of adsorption (23.6 kJ/mol). The developed pore-space-partitioned MIL-88(Co) material Co-DOBDC-TPB may have potential application to flue gas and natural gas purification.

Purely organic room-temperature phosphors, which have received extensive attention as emerging state-of-the-art luminescent materials in various fields, have a longer lifetime than fluorophores. The energy gap law and El-Sayed's rule provide clear design principles for the development of organic room-temperature phosphorescence. Therefore, the incorporation of heteroatoms (such as sulfur and phosphorus) usually promotes the intersystem crossing rate and increases the (3)(pi, pi*) configuration to realize long lifetimes. Furthermore, boron-containing phosphors not only display excellent phosphorescence properties but also expand El-Sayed's rule without (n, pi*) transitions. This review summarizes recent work on organic phosphorescence of heterocycles with boron, sulfur, and phosphorus heteroatoms and highlights the significance of the guidelines for constructing efficient phosphorescence molecules. This work is instrumental in further diversifying the pool of phosphorescent molecules and developing new and effective design strategies. [GRAPHICS] .