Gel-based room-temperature phosphorescence(RTP)materials have garnered significant attention due to their promising applications in flexible electronics and photonics.However,the inherent swollen state and porous arch...Gel-based room-temperature phosphorescence(RTP)materials have garnered significant attention due to their promising applications in flexible electronics and photonics.However,the inherent swollen state and porous architecture of such gels often promote intense molecular motion and facilitate oxygen diffusion,which can severely quench phosphorescence under ambient conditions.In this work,we report a versatile strategy for constructing high-performance organic RTP materials by leveraging organic aerogels,which exhibit superior luminescent,mechanical,and thermal properties.Owing to their structural advantages,these organic aerogels possess a three-dimensional rigid framework that enhances intersystem crossing(ISC)efficiency and promotes multiple intermolecular interactions,thereby enabling efficient RTP with an ultralong phosphorescent lifetime of up to 1007 ms.Notably,the resulting RTP aerogels demonstrate exceptional structural robustness(compression modulus of 1 MPa),excellent thermal insulation(peak heat release rate reduced to 31.1 kW/m^(2)),and outstanding flame retardancy(limiting oxygen index exceeding 90%),positioning them among the most multifunctional organic aerogels reported to date.Given their balanced combination of RTP performance,mechanical resilience,and thermal stability,these phosphorescent aerogels represent a highly promising platform for the development of advanced,multifunctional organic RTP materials.展开更多
Pure organic room-temperature phosphorescent(RTP)polymers possess good processability and flexibility over small molecular crystals.However,most of RTP polymers reported so far are based on non-conjugated polymers,and...Pure organic room-temperature phosphorescent(RTP)polymers possess good processability and flexibility over small molecular crystals.However,most of RTP polymers reported so far are based on non-conjugated polymers,and achieving efficient phosphorescent emission in RTP conjugated polymers(CPs)remains a significant challenge.Herein,we developed two RTP CPs(P(PSe ZPh-p-Ph)and P(PSe ZPh-m-Ph))by linking the phenoselenazine units with the para-and meta-phenylene units,respectively,to form the conjugated main chains.The phenylene linker with different lingking mode manipulates the effictiveπ-conjugation of the polymer backbones.Comparing with the para-linked P(PSe ZPh-pPh),meta-linked P(PSe ZPh-m-Ph)exhibit the decreased effectiveπ-conjugation and the enhanced contribution of selenium atoms to the frontier orbitals,leading to the larger spin-orbit coupling(SOC)constants and the accelerated phosphorescence radiative decay process.The P(PSe ZPhm-Ph)achieves a phosphorescence quantum yield of 21.4%in doped polystyrene films,which is among the highest efficiencies reported to date for pure organic RTP CPs.These CPs are applied to construct phosphorescent film sensors for oxygen detection with the high quenching constants(K_(sv))up to 14.80 kPa^(-1)and low detection of limit of 0.84 ppm,demostrating the potential for application in oxygen film sensors.展开更多
Developing eco-friendly natural polymer-based room-temperature phosphorescence(RTP)materials with color-tunability and flexibility remains a crucial yet challenging task.Here,we fabricate a sustainable multicolor-tuna...Developing eco-friendly natural polymer-based room-temperature phosphorescence(RTP)materials with color-tunability and flexibility remains a crucial yet challenging task.Here,we fabricate a sustainable multicolor-tunable and flexible RTP system based on sodium carboxymethyl cellulose(Na CMC).p-Aminobenzoic acid(PABA)is doped into Na CMC matrix to facilely construct Na CMC/PABA composites.The rigid hydrogen-bonding networks formed between Na CMC and PABA significantly suppress molecular vibration and non-radiative decay,resulting in an ultralong RTP lifetime of up to 1263 ms and a bright blue afterglow lasting 11 s.By incorporating commercial fluorescent dyes fluorescein(FL),calcein(CAL),and lisamine rhodamine B(LRB)as energy acceptors into the Na CMC/PABA donor matrix,multicolor long-afterglow emissions are realized in the long-wavelength region via triplet-to-singlet Forster resonance energy transfer(TS-FRET).Moreover,large-area,multicolor and flexible Na CMC-based RTP films with excellent mechanical properties are conveniently fabricated by a doping-coating-drying approach.The developed multicolor and flexible Na CMC-based RTP materials are successfully used for advanced information encryption.This work provides a direction for developing sustainable,multicolor-tunable,and flexible natural polymer-based RTP materials.展开更多
Internal rotation of conjugated organic backbone seriously impaired room temperature phosphorescence(RTP),leading to rare realization of ultra-long afterglows with RTP lifetimes over 2 s in non-bibulous polymers.Herei...Internal rotation of conjugated organic backbone seriously impaired room temperature phosphorescence(RTP),leading to rare realization of ultra-long afterglows with RTP lifetimes over 2 s in non-bibulous polymers.Herein,N-(bromophenyl)carbazoles are cyclized to lock up phenyl-carbazol internal rotation in advance and the fused nitrogen hetero-cyclic compounds are doped into poly(methyl methacrylate)(PMMA).The results show that locking up the molecular internal rotation can achieve ultra-long RTP polymers with lifetimes over 2 s,in contrast,the unlocked molecules hardly emit RTP in PMMA.The high-lying triplet excitons can transfer the energy to low-lying organic fluorescent dyes,and the persistent multicolor afterglows including white emission can be readily modulated.This work discloses an effective and extendable dopant molecular strategy for developing high-performance ultra-long organic RTP polymers.展开更多
Pure organic materials with ultralong room-temperature phosphorescence(RTP)and persistent luminescence in broad color gamut exhibit tremendous potential and broad application prospects due to their unique optical prop...Pure organic materials with ultralong room-temperature phosphorescence(RTP)and persistent luminescence in broad color gamut exhibit tremendous potential and broad application prospects due to their unique optical properties.This article proposes a simple strategy,polyatomic synergistic effect,to endow persistent luminescent materials with ultralong lifetime and broad color-tunability through polyatomic synergistic effect and non-traditional phosphorescence resonance energy transfer(PRET).By leveraging the polyatomic synergistic effect to enhance the intersystem crossing(ISC)in bibenzimidazole(BBI)derivatives and suppress the non-radiative transition process,ultralong persistent room-temperature phosphorescence has been successfully achieved after incorporating BBI-Cl-M into poly(methyl methacrylate)(PMMA)to form a rigid matrix(BBI-Cl-M@PMMA).Specifically,the ester functionalized bibenzimidazole with modified chlorine on molecular skeleton(BBI-Cl-M)demonstrates a remarkable phosphorescent lifetime(τp)of up to 256.4 ms.In addition,the behaviors and mechanism of RTP via polyatomic synergistic effect have been further understood by theoretical calculation and single crystal analysis.Subsequently,utilizing BBI-Cl-M as the energy donor and Rhodamine B(RB)as the energy acceptor,persistent and multicolor organic afterglow covering from green to red has been realized successfully by simply regulating the doping composition and concentration of PRET systems.These RTP materials have also been applied in underwater afterglow emission and multilevel anti-counterfeiting technology successfully.展开更多
Room-temperature phosphorescence(RTP)materials exhibiting long emission lifetimes have gained increasing attention owing to their potential applications in encryption,anti-counterfeiting,and sensing.However,most polym...Room-temperature phosphorescence(RTP)materials exhibiting long emission lifetimes have gained increasing attention owing to their potential applications in encryption,anti-counterfeiting,and sensing.However,most polymers exhibit a short RTP lifetime(<1 s)because of their unstable triplet excitons.Herein,a new strategy of polymer chain stabilized phosphorescence(PCSP),which yields a new kind of RTP polymers with an ultralong lifetime and a sensitive oxygen response,has been reported.The rigid polymer chains of poly(methyl mathacrylate)(PMMA)immobilize the emitter molecules through multiple interactions between them,giving rise to efficient RTP.Meanwhile,the loosely-packed amorphous polymer chains allow oxygen to diffuse inside,endowing the doped polymers with oxygen sensitivity.Flexible and transparent polymer films exhibited an impressive ultralong RTP lifetime of 2.57 s at room temperature in vacuum,which was among the best performance of PMMA.Intriguingly,their RTP was rapidly quenched in the presence of oxygen.Furthermore,RTP microparticles with a diameter of 1.63μm were synthesized using in situ dispersion polymerization technique.Finally,oxygen sensors for quick,visual,and quantitative oxygen detection were developed based on the RTP microparticles through phosphorescence lifetime and image analysis.With distinctive advantages such as an ultralong lifetime,oxygen sensitivity,ease of fabrication,and cost-effectiveness,PCSP opens a new avenue to sensitive materials for oxygen detection.展开更多
Phosphorus-based luminescent materials consist of certain phosphorus in the aromatic backbones,endowing a larger nuclear charge(Z,15P),rich valence states for the phosphorus core,and various electron geometries.These ...Phosphorus-based luminescent materials consist of certain phosphorus in the aromatic backbones,endowing a larger nuclear charge(Z,15P),rich valence states for the phosphorus core,and various electron geometries.These features enable promising exploitation for luminescent materials with significant quantum efficiencies and tunable singlet and triplet populations.This mini review focuses on the break-throughs of organic and organometallic phosphorus compounds in advanced circularly polarized fluorescence(CPF)and circularly polarized room-temperature phosphorescence(CP-RTP)by unveiling the structure-function relationships,e.g.,design concept,charge transfer(CT)type,chiral conformation,and excited state transition configuration,and the recent applications in optical information encryption,lighting-displaying,and organic light emitting diodes(OLEDs).By dedicated analysis of current progresses,we hope this work will throw insights into phosphorus-based CPF and CP-RTP behaviors and provide a reference for the rational design of high-performance phosphorus-based emitters.展开更多
Non-covalent interactions-driven host-vip assembly based on metallo-tweezers has been used to construct varied optical functional materials with attractive structures and properties.We reported here two pairs of chi...Non-covalent interactions-driven host-vip assembly based on metallo-tweezers has been used to construct varied optical functional materials with attractive structures and properties.We reported here two pairs of chiral gold(Ⅰ)-based metallo-tweezers as hosts to clip Ag^(Ⅰ)or Cu^(Ⅰ)cations for circularly polarized phosphorescence(CPP),driven by the integration of two-fold coordination and heterometallophilic interactions.The Au^(Ⅰ)-based hosts and metal ions-vips formed sandwich structures in 1:1 ratio with high binding affinity.The achieved tweezer/cation adducts exhibited red-shifted absorption bands and circular dichroism signals,which were attributed to the newly formed ligand to metal-metal charge transfer process.Remarkably,the host-vip supramolecular adducts showed turn-on phosphorescence and CPP,which benefited from rigidifying effect of multiple intermolecular interactions and shorter excited-state lifetime.Overall,our findings bring new insights into the feasibility to achieve and modulate CPP performance by fabricating metallo-tweezer-based host-vip complexes.展开更多
Stimulus-responsive organic room temperature phosphorescent(RTP)materials have received significant attention in bioimaging,sensing,and data storage because of their controllable dynamic variability and rapid response...Stimulus-responsive organic room temperature phosphorescent(RTP)materials have received significant attention in bioimaging,sensing,and data storage because of their controllable dynamic variability and rapid response.Organic cocrystals,with tailor-designed optical properties through manipulation of their aggregate structures,have proven to be very effective in elucidating the structureproperty relationship of organic RTP materials at the molecular level.Therefore,enhancing RTP through rigid frameworks that promote intersystem crossing is a valid approach.Notably,the realization of organic RTP co-crystal performance by altering the components or adjusting the crystal lattices is highly appealing;however,this has not been fully addressed.In this study,an organic RTP cocrystal,4,40-bipyridine(44BD),was employed as the host,and 1,4-diiodotetrafluorobenzene(DITF)and 4-bromo-2,3,5,6-tetrafluorobenzoic acid(TFBA)were employed as vips.The 44BD-DITF co-crystal exhibited an orange RTP,whereas 44BD-TFBA displayed a bright yellow RTP.Crystal analysis and theoretical calculations revealed that dense molecular packing and abundant intermolecular interactions within these co-crystals are crucial for the emergence of RTP.Notably,both co-crystals show a reversible acid/base stimulus response,that is,exposure to hydrochloric acid(HCl)fumes results in quenching of their RTP,which can be subsequently restored by triethylamine(TEA)fumigation.This study presents an effective approach towards reversible RTP switching in organic co-crystals,thus offering opportunities for the development of acid/base stimulus-responsive materials for next-generation applications.展开更多
Purely organic room-temperature phosphorescence(RTP)and fluorescence dual-emission materials in aqueous solution have attracted growing attention.Herein,we report a fluorescencephosphorescence dual emission host-vip...Purely organic room-temperature phosphorescence(RTP)and fluorescence dual-emission materials in aqueous solution have attracted growing attention.Herein,we report a fluorescencephosphorescence dual emission host-vip complex by simple assembly of cucurbit[8]uril(CB[8])and4-(4-bromophenyl)pyridinium derivative in water.Macrocyclic confinement and unique 1:2 host-vip structure could effectively inhibit non-radiative transition of the vip and the quenching of water molecule,thus induce effective RTP emission in water(τ_(RTP)=0.472 ms,Φ_(RTP)=1.37%).Specifically,based on competitive binding,this host-vip complex exhibits rapid ratiometric luminescent detection behavior to 3-nitrotyrosine,a specific biomarker of kidney injury,with a low limit of detection of 10.7 nmol/L.This work highlights the great potential of macrocyclic-confinement-derived RTP materials in biomarker detection,and will undoubtedly broaden the utilization scope of RTP.展开更多
This review summarizes the recent progress of efficient room temperature phosphorescence（RTP） from pure organic luminogens achieved by crystallization-induced phosphorescence（CIP）,with focus on the advances in our...This review summarizes the recent progress of efficient room temperature phosphorescence（RTP） from pure organic luminogens achieved by crystallization-induced phosphorescence（CIP）,with focus on the advances in our group.Besides homocrystals,mixed crystals and cocrystals are also discussed.Meanwhile,intriguing RTP emission from the luminogens without conventional chromophores is demonstrated.展开更多
Pure organic luminogens with efficient room temperature phosphorescence（RTP） and remarkable mechanochromism are highly desired in view of their fundamental significance and technical applications. Herein, four twist...Pure organic luminogens with efficient room temperature phosphorescence（RTP） and remarkable mechanochromism are highly desired in view of their fundamental significance and technical applications. Herein, four twisted pure organic luminogens based on benzophenone and aromatic amines were synthesized and their photophysical properties were thoroughly investigated. They exhibit crystallization-induced phosphorescence（CIP）, giving bright fluorescence and phosphorescence dual emission in crystals. Upon grinding, they become amorphous and emit predominantly red-shifted fluorescence, demonstrating remarkable mechanochromism. Furthermore, three of them even demonstrate greatly enhanced emission upon grinding, which is rarely observed in twisted D-A structured luminogens.展开更多
Amber can emit room temperature phosphorescence(RTP)under the well-known 365 nm fluorescence ultraviolet light.This paper is devoted to the phosphorescence study of 20 pieces of amber materials from the Dominican Repu...Amber can emit room temperature phosphorescence(RTP)under the well-known 365 nm fluorescence ultraviolet light.This paper is devoted to the phosphorescence study of 20 pieces of amber materials from the Dominican Republic,Mexico,Baltic sea,Myanmar,and Fushun,China.The results show that amber from the same geographic origin has similar shape in phosphorescence spectra.However,the shape of the amber phosphorescence spectra varies depending on their different localities.Burmite(amber from Myanmar)and Fushun amber have a bright yellow phosphorescence with a long lifetime,while the Dominican and Mexican ones are weaker and last shorter.The irradiation of Baltic amber becomes faint or even inert.Phosphorescence spectral Gaussian fitting results suggest an emission maximum near 550 nm in most amber samples.Their phosphorescence lifetime,analyzed through the exponential function fitting,is up to 1 second in Burmite and Fushun samples,shorter in the Dominican and Mexican ones,about 0.230 s,and the shortest in Baltic amber,close to 0.151 s.These variations of phosphorescence lifetime and intensity are related to the relative geological ages of these amber.It indicated that the phosphorescence agent was probably formed during the long geological time.While the anomaly occurred in Baltic amber,the only one found in a sea secondary deposit form,it demonstrated that the terrestrial geological environment these amber preserved has prevented the phosphorescence agent to be deactivated.展开更多
Room temperature phosphorescence(RTP) has drawn increasing attention for its great potential in practical applications.Polymers with large molecular weights and long chains tend to form coil, which can endow them with...Room temperature phosphorescence(RTP) has drawn increasing attention for its great potential in practical applications.Polymers with large molecular weights and long chains tend to form coil, which can endow them with a high degree of possible rigidity and result in the much restricted non-radiative transition. Also, the intertwined structure of polymers could isolate the oxygen and humidity effectively, thus reducing the consumption of triplet excitons. In consideration of these points, organic polymers would be another kind of ideal platform to realize RTP effect. This short review summarized the design strategy of the purely organic room temperature phosphorescence polymers, mainly focusing on the building forms of polymers and the corresponding inherent mechanisms,and also gives some outlooks on the further exploration of this field at the end of this paper.展开更多
Long-lasting phosphorescence （LLP） was observed in Ce-doped Y3Al5O12 phosphors synthesized in reducing atmosphere. The characteristic emission of the 2D–2F5/2 and 2D–2F7/2 transition of Ce3＋ in photoluminescence ...Long-lasting phosphorescence （LLP） was observed in Ce-doped Y3Al5O12 phosphors synthesized in reducing atmosphere. The characteristic emission of the 2D–2F5/2 and 2D–2F7/2 transition of Ce3＋ in photoluminescence （PL） and LLP spectra was studied. It was interesting that the ratio between the peak areas of 2D–2F5/2 and 2D–2F 7/2 transitions in the PL spectrum was different from the ratio of that in LLP emission spectrum. And the ratios had different change regularities with increased Ce3＋ concentration. The possible reason was attributed to the defect in the YAG host,which was affected by increasing the Ce3＋ concentration. There were indications that the defect in the Ce3＋-doped YAG samples was strongly associated with oxygen vacancy. And the defect levels were studied through thermoluminescence （TL） experiment. The results showed that the trap depth was between 0.6 and 0.65 eV,and the kinetic order of the LLP was 2.展开更多
The phosphors of the alkaline earth aluminates coactivated with europium and other rare earths were successfully obtained by microwave radiation heating technique.These phosphors have bright phosphorescence and maint...The phosphors of the alkaline earth aluminates coactivated with europium and other rare earths were successfully obtained by microwave radiation heating technique.These phosphors have bright phosphorescence and maintain their afterglow for a fairly long duration.展开更多
Pure organic room temperature phosphorescence(RTP) has been attracting a lot interest recently. So far,many strategies have succeeded in achieving efficient organic RTP materials by increasing the rate of intersystem ...Pure organic room temperature phosphorescence(RTP) has been attracting a lot interest recently. So far,many strategies have succeeded in achieving efficient organic RTP materials by increasing the rate of intersystem crossing(ISC) and suppressing non-radiative transitions. In supramolecular chemistry, the control and regulation of molecular recognition based on the role of the host and vip in supramolecular polymers matrix, has attracted much attention. Recently, researchers have successfully achieved room temperature phosphorescence of pure organic complexes through host-vip interactions. The host molecule specifically includes the phosphorescent vip to reduce non-radiative transitions and enhance room temperature phosphorescence emission. This review aims to describe the developments and achievements of pure organic room temperature phosphorescence systems through the mechanism of host-vip interactions in recent years, and demonstrates the exploration and pursuit of phosphorescent materials of researchers in different fields.展开更多
A purely organic D-π-A-π-D type emitter showing thermally activated delayed fluorescence(TADF)and room temperature phosphorescence(RTP)was designed and synthesized by utilizing the benzophenone as an acceptor and th...A purely organic D-π-A-π-D type emitter showing thermally activated delayed fluorescence(TADF)and room temperature phosphorescence(RTP)was designed and synthesized by utilizing the benzophenone as an acceptor and the N-phenyl-2-napthylamine as a donor moiety.It exhibits considerable TADF character in doped PMMA film and room temperature phosphorescence with a long lifetime of 74 ms at466 nm in solid state.The devices with the configuration of ITO/Mo_(2) O_(3)(4 nm)/mCP(30 nm)/mCP:x wt%NP2 BP/TmTyPB(60 nm)/LiF(1.5 nm)/AI(100 nm)were prepared by vacuum evaporation to explore their electroluminescent performance.Intere stingly,the non-doped device has obtained near-white emission with a fluorescence emission peak at 475 nm and a phosphore scence emission peak at 563 nm having the CIE coordinate of(0.23,0.32)and the maximum external quantum efficiency of 1.09%.展开更多
A new aluminosilicate long-lasting phosphor with composition of NaA1SiO4：Eu2＋,Ho3＋ was synthesized and investigated. Under UV light excitation, the phosphor emitted yellow light corresponding to the characteristic ...A new aluminosilicate long-lasting phosphor with composition of NaA1SiO4：Eu2＋,Ho3＋ was synthesized and investigated. Under UV light excitation, the phosphor emitted yellow light corresponding to the characteristic emission of Eu2＋ due to 5d-4f transi- tion. Bright yellow phosphorescence sustaining for more than 30 rain was observed after ceasing the excitation. The phosphorescence intensity decay obeyed a fl decay law, indicating a tunneling electron-hole recombination process in the phosphor. Four peaks ap- peared in the thermoluminescence curve and the ones at 322 and 370 K were thought to account for the long lasting phosphorescence at room temperature. The Ho3＋ ion incorporated into the phosphor did not give any light but dramatically increased the intensities of both photoluminescence and phosphorescence via promoting defect levels in the phosphor.展开更多
Room-temperature phosphorescence（RTP） materials have attracted great attention due to their involvement of excited triplet states and comparatively long decay lifetimes.In this short review,recent progress on enhanc...Room-temperature phosphorescence（RTP） materials have attracted great attention due to their involvement of excited triplet states and comparatively long decay lifetimes.In this short review,recent progress on enhancement of RTP from purely organic materials is summarized.According to the mechanism of phosphorescence emission,two principles are discussed to construct efficient RTP materials：one is promoting intersystem crossing（ISC） efficiency by using aromatic carbonyl,heavyatom,or/and heterocycle/heteroatom containing compounds;the other is suppressing intramolecular motion and intermolecular collision which can quench excited triplet states,including embedding phosphors into polymers and packing them tightly in crystals.With aforementioned strategies,RTP from purely organic materials was achieved both in fluid and rigid media.展开更多
基金supported by the National Natural Science Foundation of China(22475172 and 52203242)the Zhejiang Provincial Natural Science Foundation of China(LQ23B020004)the Fundamental Research Funds for the Central Universities.
文摘Gel-based room-temperature phosphorescence(RTP)materials have garnered significant attention due to their promising applications in flexible electronics and photonics.However,the inherent swollen state and porous architecture of such gels often promote intense molecular motion and facilitate oxygen diffusion,which can severely quench phosphorescence under ambient conditions.In this work,we report a versatile strategy for constructing high-performance organic RTP materials by leveraging organic aerogels,which exhibit superior luminescent,mechanical,and thermal properties.Owing to their structural advantages,these organic aerogels possess a three-dimensional rigid framework that enhances intersystem crossing(ISC)efficiency and promotes multiple intermolecular interactions,thereby enabling efficient RTP with an ultralong phosphorescent lifetime of up to 1007 ms.Notably,the resulting RTP aerogels demonstrate exceptional structural robustness(compression modulus of 1 MPa),excellent thermal insulation(peak heat release rate reduced to 31.1 kW/m^(2)),and outstanding flame retardancy(limiting oxygen index exceeding 90%),positioning them among the most multifunctional organic aerogels reported to date.Given their balanced combination of RTP performance,mechanical resilience,and thermal stability,these phosphorescent aerogels represent a highly promising platform for the development of advanced,multifunctional organic RTP materials.
基金supported by the National Natural Science Foundation of China(Nos.22275182,22075272,51973211,51833009,21674111 and 52261135541)the Ministry of Science and Technology of the People’s Republic of China(the National Key R&D Program of China,No.2022YFB4200400)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB0520102)。
文摘Pure organic room-temperature phosphorescent(RTP)polymers possess good processability and flexibility over small molecular crystals.However,most of RTP polymers reported so far are based on non-conjugated polymers,and achieving efficient phosphorescent emission in RTP conjugated polymers(CPs)remains a significant challenge.Herein,we developed two RTP CPs(P(PSe ZPh-p-Ph)and P(PSe ZPh-m-Ph))by linking the phenoselenazine units with the para-and meta-phenylene units,respectively,to form the conjugated main chains.The phenylene linker with different lingking mode manipulates the effictiveπ-conjugation of the polymer backbones.Comparing with the para-linked P(PSe ZPh-pPh),meta-linked P(PSe ZPh-m-Ph)exhibit the decreased effectiveπ-conjugation and the enhanced contribution of selenium atoms to the frontier orbitals,leading to the larger spin-orbit coupling(SOC)constants and the accelerated phosphorescence radiative decay process.The P(PSe ZPhm-Ph)achieves a phosphorescence quantum yield of 21.4%in doped polystyrene films,which is among the highest efficiencies reported to date for pure organic RTP CPs.These CPs are applied to construct phosphorescent film sensors for oxygen detection with the high quenching constants(K_(sv))up to 14.80 kPa^(-1)and low detection of limit of 0.84 ppm,demostrating the potential for application in oxygen film sensors.
基金supported by the National Natural Science Foundation of China(No.51503094)Natural Science Foundation of Shandong Province(Nos.ZR2021ME149 and ZR2021ME126)+1 种基金Shandong Province Science and Technology-based Small and Medium-sized Enterprises Innovation Capacity Enhancement Project(No.2024TSGC0965)Research Foundation of Liaocheng University(No.318011905)。
文摘Developing eco-friendly natural polymer-based room-temperature phosphorescence(RTP)materials with color-tunability and flexibility remains a crucial yet challenging task.Here,we fabricate a sustainable multicolor-tunable and flexible RTP system based on sodium carboxymethyl cellulose(Na CMC).p-Aminobenzoic acid(PABA)is doped into Na CMC matrix to facilely construct Na CMC/PABA composites.The rigid hydrogen-bonding networks formed between Na CMC and PABA significantly suppress molecular vibration and non-radiative decay,resulting in an ultralong RTP lifetime of up to 1263 ms and a bright blue afterglow lasting 11 s.By incorporating commercial fluorescent dyes fluorescein(FL),calcein(CAL),and lisamine rhodamine B(LRB)as energy acceptors into the Na CMC/PABA donor matrix,multicolor long-afterglow emissions are realized in the long-wavelength region via triplet-to-singlet Forster resonance energy transfer(TS-FRET).Moreover,large-area,multicolor and flexible Na CMC-based RTP films with excellent mechanical properties are conveniently fabricated by a doping-coating-drying approach.The developed multicolor and flexible Na CMC-based RTP materials are successfully used for advanced information encryption.This work provides a direction for developing sustainable,multicolor-tunable,and flexible natural polymer-based RTP materials.
文摘Internal rotation of conjugated organic backbone seriously impaired room temperature phosphorescence(RTP),leading to rare realization of ultra-long afterglows with RTP lifetimes over 2 s in non-bibulous polymers.Herein,N-(bromophenyl)carbazoles are cyclized to lock up phenyl-carbazol internal rotation in advance and the fused nitrogen hetero-cyclic compounds are doped into poly(methyl methacrylate)(PMMA).The results show that locking up the molecular internal rotation can achieve ultra-long RTP polymers with lifetimes over 2 s,in contrast,the unlocked molecules hardly emit RTP in PMMA.The high-lying triplet excitons can transfer the energy to low-lying organic fluorescent dyes,and the persistent multicolor afterglows including white emission can be readily modulated.This work discloses an effective and extendable dopant molecular strategy for developing high-performance ultra-long organic RTP polymers.
基金supported by the National Natural Science Foundation of China(NSFC,Nos.22061039,22165027)the Top Leading Talents Project of Gansu Province,the Key R&D program of Gansu Province(No.21YF5GA066)+1 种基金Gansu Province College Industry Support Plan Project(No.2022CYZC-18)Northwest Normal University 2023 graduate research funding project(No.2023KYZZS154)。
文摘Pure organic materials with ultralong room-temperature phosphorescence(RTP)and persistent luminescence in broad color gamut exhibit tremendous potential and broad application prospects due to their unique optical properties.This article proposes a simple strategy,polyatomic synergistic effect,to endow persistent luminescent materials with ultralong lifetime and broad color-tunability through polyatomic synergistic effect and non-traditional phosphorescence resonance energy transfer(PRET).By leveraging the polyatomic synergistic effect to enhance the intersystem crossing(ISC)in bibenzimidazole(BBI)derivatives and suppress the non-radiative transition process,ultralong persistent room-temperature phosphorescence has been successfully achieved after incorporating BBI-Cl-M into poly(methyl methacrylate)(PMMA)to form a rigid matrix(BBI-Cl-M@PMMA).Specifically,the ester functionalized bibenzimidazole with modified chlorine on molecular skeleton(BBI-Cl-M)demonstrates a remarkable phosphorescent lifetime(τp)of up to 256.4 ms.In addition,the behaviors and mechanism of RTP via polyatomic synergistic effect have been further understood by theoretical calculation and single crystal analysis.Subsequently,utilizing BBI-Cl-M as the energy donor and Rhodamine B(RB)as the energy acceptor,persistent and multicolor organic afterglow covering from green to red has been realized successfully by simply regulating the doping composition and concentration of PRET systems.These RTP materials have also been applied in underwater afterglow emission and multilevel anti-counterfeiting technology successfully.
基金National Natural Science Foundation of China(No.22475241)Guangdong Basic and Applied Basic Research Foundation(Nos.2022A1515010826 and 2023A1515012696)the Fundamental Research Funds for the Central Universities(Nos.17lgjc03 and 18lgpy04).
文摘Room-temperature phosphorescence(RTP)materials exhibiting long emission lifetimes have gained increasing attention owing to their potential applications in encryption,anti-counterfeiting,and sensing.However,most polymers exhibit a short RTP lifetime(<1 s)because of their unstable triplet excitons.Herein,a new strategy of polymer chain stabilized phosphorescence(PCSP),which yields a new kind of RTP polymers with an ultralong lifetime and a sensitive oxygen response,has been reported.The rigid polymer chains of poly(methyl mathacrylate)(PMMA)immobilize the emitter molecules through multiple interactions between them,giving rise to efficient RTP.Meanwhile,the loosely-packed amorphous polymer chains allow oxygen to diffuse inside,endowing the doped polymers with oxygen sensitivity.Flexible and transparent polymer films exhibited an impressive ultralong RTP lifetime of 2.57 s at room temperature in vacuum,which was among the best performance of PMMA.Intriguingly,their RTP was rapidly quenched in the presence of oxygen.Furthermore,RTP microparticles with a diameter of 1.63μm were synthesized using in situ dispersion polymerization technique.Finally,oxygen sensors for quick,visual,and quantitative oxygen detection were developed based on the RTP microparticles through phosphorescence lifetime and image analysis.With distinctive advantages such as an ultralong lifetime,oxygen sensitivity,ease of fabrication,and cost-effectiveness,PCSP opens a new avenue to sensitive materials for oxygen detection.
基金supported by the National Natural Science Foundation of China(No.21871133)the Natural Science Foundation of Jiangsu Province(No.BK20211146)the Science,Technology,and Innovation Commission of Shenzhen Municipality(No.JCYJ20180307153251975)。
文摘Phosphorus-based luminescent materials consist of certain phosphorus in the aromatic backbones,endowing a larger nuclear charge(Z,15P),rich valence states for the phosphorus core,and various electron geometries.These features enable promising exploitation for luminescent materials with significant quantum efficiencies and tunable singlet and triplet populations.This mini review focuses on the break-throughs of organic and organometallic phosphorus compounds in advanced circularly polarized fluorescence(CPF)and circularly polarized room-temperature phosphorescence(CP-RTP)by unveiling the structure-function relationships,e.g.,design concept,charge transfer(CT)type,chiral conformation,and excited state transition configuration,and the recent applications in optical information encryption,lighting-displaying,and organic light emitting diodes(OLEDs).By dedicated analysis of current progresses,we hope this work will throw insights into phosphorus-based CPF and CP-RTP behaviors and provide a reference for the rational design of high-performance phosphorus-based emitters.
基金financially supported by the National Natural Science Foundation of China(Nos.92356304,92061201,and 22105177)the National Key R&D Program of China(No.2021YFA1200301)+1 种基金the China Postdoctoral Science Foundation(No.2021TQ0294)the Zhongyuan Thousand Talents(Zhongyuan Scholars)Program of Henan Province(No.234000510007)。
文摘Non-covalent interactions-driven host-vip assembly based on metallo-tweezers has been used to construct varied optical functional materials with attractive structures and properties.We reported here two pairs of chiral gold(Ⅰ)-based metallo-tweezers as hosts to clip Ag^(Ⅰ)or Cu^(Ⅰ)cations for circularly polarized phosphorescence(CPP),driven by the integration of two-fold coordination and heterometallophilic interactions.The Au^(Ⅰ)-based hosts and metal ions-vips formed sandwich structures in 1:1 ratio with high binding affinity.The achieved tweezer/cation adducts exhibited red-shifted absorption bands and circular dichroism signals,which were attributed to the newly formed ligand to metal-metal charge transfer process.Remarkably,the host-vip supramolecular adducts showed turn-on phosphorescence and CPP,which benefited from rigidifying effect of multiple intermolecular interactions and shorter excited-state lifetime.Overall,our findings bring new insights into the feasibility to achieve and modulate CPP performance by fabricating metallo-tweezer-based host-vip complexes.
基金supported by the Natural Science Foundation of Jilin Province(20240101003JC)the Department of Science and Technology of Jilin Province(20230508176RC and 20240602063RC)+1 种基金the China Postdoctoral Science Foundation(2024M751080 and 2024T170337)the National Natural Science Foundation of China(52073116,22275065,22302073).
文摘Stimulus-responsive organic room temperature phosphorescent(RTP)materials have received significant attention in bioimaging,sensing,and data storage because of their controllable dynamic variability and rapid response.Organic cocrystals,with tailor-designed optical properties through manipulation of their aggregate structures,have proven to be very effective in elucidating the structureproperty relationship of organic RTP materials at the molecular level.Therefore,enhancing RTP through rigid frameworks that promote intersystem crossing is a valid approach.Notably,the realization of organic RTP co-crystal performance by altering the components or adjusting the crystal lattices is highly appealing;however,this has not been fully addressed.In this study,an organic RTP cocrystal,4,40-bipyridine(44BD),was employed as the host,and 1,4-diiodotetrafluorobenzene(DITF)and 4-bromo-2,3,5,6-tetrafluorobenzoic acid(TFBA)were employed as vips.The 44BD-DITF co-crystal exhibited an orange RTP,whereas 44BD-TFBA displayed a bright yellow RTP.Crystal analysis and theoretical calculations revealed that dense molecular packing and abundant intermolecular interactions within these co-crystals are crucial for the emergence of RTP.Notably,both co-crystals show a reversible acid/base stimulus response,that is,exposure to hydrochloric acid(HCl)fumes results in quenching of their RTP,which can be subsequently restored by triethylamine(TEA)fumigation.This study presents an effective approach towards reversible RTP switching in organic co-crystals,thus offering opportunities for the development of acid/base stimulus-responsive materials for next-generation applications.
基金financially supported by the National Natural Science Foundation of China(Nos.22171069 and 21871075)the Educational Committee of Hebei Province(No.JZX2024012)the Tianjin Natural Science Foundation(No.23JCYBJC00800)。
文摘Purely organic room-temperature phosphorescence(RTP)and fluorescence dual-emission materials in aqueous solution have attracted growing attention.Herein,we report a fluorescencephosphorescence dual emission host-vip complex by simple assembly of cucurbit[8]uril(CB[8])and4-(4-bromophenyl)pyridinium derivative in water.Macrocyclic confinement and unique 1:2 host-vip structure could effectively inhibit non-radiative transition of the vip and the quenching of water molecule,thus induce effective RTP emission in water(τ_(RTP)=0.472 ms,Φ_(RTP)=1.37%).Specifically,based on competitive binding,this host-vip complex exhibits rapid ratiometric luminescent detection behavior to 3-nitrotyrosine,a specific biomarker of kidney injury,with a low limit of detection of 10.7 nmol/L.This work highlights the great potential of macrocyclic-confinement-derived RTP materials in biomarker detection,and will undoubtedly broaden the utilization scope of RTP.
基金financially supported by the National Natural Science Foundation of China(No.51473092)the Shanghai Rising-Star Program(No.15QA1402500)the SMC-Chenxing Young Scholar Program of Shanghai Jiao Tong University
文摘This review summarizes the recent progress of efficient room temperature phosphorescence（RTP） from pure organic luminogens achieved by crystallization-induced phosphorescence（CIP）,with focus on the advances in our group.Besides homocrystals,mixed crystals and cocrystals are also discussed.Meanwhile,intriguing RTP emission from the luminogens without conventional chromophores is demonstrated.
基金financially supported by the National Natural Science Foundation of China (No. 51473092)
文摘Pure organic luminogens with efficient room temperature phosphorescence（RTP） and remarkable mechanochromism are highly desired in view of their fundamental significance and technical applications. Herein, four twisted pure organic luminogens based on benzophenone and aromatic amines were synthesized and their photophysical properties were thoroughly investigated. They exhibit crystallization-induced phosphorescence（CIP）, giving bright fluorescence and phosphorescence dual emission in crystals. Upon grinding, they become amorphous and emit predominantly red-shifted fluorescence, demonstrating remarkable mechanochromism. Furthermore, three of them even demonstrate greatly enhanced emission upon grinding, which is rarely observed in twisted D-A structured luminogens.
基金the financial support from the National Key R&D Program of China(2018YFF0215400)grants from the Gemmological Institute of the China University of Geosciences in Wuhan。
文摘Amber can emit room temperature phosphorescence(RTP)under the well-known 365 nm fluorescence ultraviolet light.This paper is devoted to the phosphorescence study of 20 pieces of amber materials from the Dominican Republic,Mexico,Baltic sea,Myanmar,and Fushun,China.The results show that amber from the same geographic origin has similar shape in phosphorescence spectra.However,the shape of the amber phosphorescence spectra varies depending on their different localities.Burmite(amber from Myanmar)and Fushun amber have a bright yellow phosphorescence with a long lifetime,while the Dominican and Mexican ones are weaker and last shorter.The irradiation of Baltic amber becomes faint or even inert.Phosphorescence spectral Gaussian fitting results suggest an emission maximum near 550 nm in most amber samples.Their phosphorescence lifetime,analyzed through the exponential function fitting,is up to 1 second in Burmite and Fushun samples,shorter in the Dominican and Mexican ones,about 0.230 s,and the shortest in Baltic amber,close to 0.151 s.These variations of phosphorescence lifetime and intensity are related to the relative geological ages of these amber.It indicated that the phosphorescence agent was probably formed during the long geological time.While the anomaly occurred in Baltic amber,the only one found in a sea secondary deposit form,it demonstrated that the terrestrial geological environment these amber preserved has prevented the phosphorescence agent to be deactivated.
基金financially supported by the National Natural Science Foundation of China (No. 21734007)Tianjin government
文摘Room temperature phosphorescence(RTP) has drawn increasing attention for its great potential in practical applications.Polymers with large molecular weights and long chains tend to form coil, which can endow them with a high degree of possible rigidity and result in the much restricted non-radiative transition. Also, the intertwined structure of polymers could isolate the oxygen and humidity effectively, thus reducing the consumption of triplet excitons. In consideration of these points, organic polymers would be another kind of ideal platform to realize RTP effect. This short review summarized the design strategy of the purely organic room temperature phosphorescence polymers, mainly focusing on the building forms of polymers and the corresponding inherent mechanisms,and also gives some outlooks on the further exploration of this field at the end of this paper.
基金Project supported by National Basic Research Program of China (2007CB935502)National Natural Science Foundation of China (20921002)
文摘Long-lasting phosphorescence （LLP） was observed in Ce-doped Y3Al5O12 phosphors synthesized in reducing atmosphere. The characteristic emission of the 2D–2F5/2 and 2D–2F7/2 transition of Ce3＋ in photoluminescence （PL） and LLP spectra was studied. It was interesting that the ratio between the peak areas of 2D–2F5/2 and 2D–2F 7/2 transitions in the PL spectrum was different from the ratio of that in LLP emission spectrum. And the ratios had different change regularities with increased Ce3＋ concentration. The possible reason was attributed to the defect in the YAG host,which was affected by increasing the Ce3＋ concentration. There were indications that the defect in the Ce3＋-doped YAG samples was strongly associated with oxygen vacancy. And the defect levels were studied through thermoluminescence （TL） experiment. The results showed that the trap depth was between 0.6 and 0.65 eV,and the kinetic order of the LLP was 2.
文摘The phosphors of the alkaline earth aluminates coactivated with europium and other rare earths were successfully obtained by microwave radiation heating technique.These phosphors have bright phosphorescence and maintain their afterglow for a fairly long duration.
基金financial support from the National Natural Science Foundation of China (NSFC) (Nos. 21788102, 21722603 and 21871083)Project supported by Shanghai Municipal Science and Technology Major Project (No. 2018SHZDZX03)+2 种基金the Innovation Program of Shanghai Municipal Education Commission (No. 2017-01-07-00-02-E00010)State Key Laboratory for Modification of Chemical Fibers and Polymer Materials (No. KF1803)Donghua University and the Fundamental Research Funds (No. KF1803) for the Central Universities
文摘Pure organic room temperature phosphorescence(RTP) has been attracting a lot interest recently. So far,many strategies have succeeded in achieving efficient organic RTP materials by increasing the rate of intersystem crossing(ISC) and suppressing non-radiative transitions. In supramolecular chemistry, the control and regulation of molecular recognition based on the role of the host and vip in supramolecular polymers matrix, has attracted much attention. Recently, researchers have successfully achieved room temperature phosphorescence of pure organic complexes through host-vip interactions. The host molecule specifically includes the phosphorescent vip to reduce non-radiative transitions and enhance room temperature phosphorescence emission. This review aims to describe the developments and achievements of pure organic room temperature phosphorescence systems through the mechanism of host-vip interactions in recent years, and demonstrates the exploration and pursuit of phosphorescent materials of researchers in different fields.
基金absolutely supported by Program for National Natural Scientific Foundation of China(Nos.91833304,61904120,61775155,61705158)Natural Science Foundation of Shanxi Province(Nos.201901D211090,201903D121100,201801D221124)+1 种基金the Fundamental Research Funds for the Central Universities,Shanxi Provincial Key Innovative Research Team in Science and Technology(No.201601D021043)the Joint Research Funds of Department of Science&Technology of Shaanxi Province and Northwestern Polytechnical University(No.2020GXLH-Z-006)。
文摘A purely organic D-π-A-π-D type emitter showing thermally activated delayed fluorescence(TADF)and room temperature phosphorescence(RTP)was designed and synthesized by utilizing the benzophenone as an acceptor and the N-phenyl-2-napthylamine as a donor moiety.It exhibits considerable TADF character in doped PMMA film and room temperature phosphorescence with a long lifetime of 74 ms at466 nm in solid state.The devices with the configuration of ITO/Mo_(2) O_(3)(4 nm)/mCP(30 nm)/mCP:x wt%NP2 BP/TmTyPB(60 nm)/LiF(1.5 nm)/AI(100 nm)were prepared by vacuum evaporation to explore their electroluminescent performance.Intere stingly,the non-doped device has obtained near-white emission with a fluorescence emission peak at 475 nm and a phosphore scence emission peak at 563 nm having the CIE coordinate of(0.23,0.32)and the maximum external quantum efficiency of 1.09%.
基金Project supported by the Funds for Creative Research Groups of China(21221061)
文摘A new aluminosilicate long-lasting phosphor with composition of NaA1SiO4：Eu2＋,Ho3＋ was synthesized and investigated. Under UV light excitation, the phosphor emitted yellow light corresponding to the characteristic emission of Eu2＋ due to 5d-4f transi- tion. Bright yellow phosphorescence sustaining for more than 30 rain was observed after ceasing the excitation. The phosphorescence intensity decay obeyed a fl decay law, indicating a tunneling electron-hole recombination process in the phosphor. Four peaks ap- peared in the thermoluminescence curve and the ones at 322 and 370 K were thought to account for the long lasting phosphorescence at room temperature. The Ho3＋ ion incorporated into the phosphor did not give any light but dramatically increased the intensities of both photoluminescence and phosphorescence via promoting defect levels in the phosphor.
基金the financial support from The National Basic Research Program of China(No.2014CB643802)Ministry of Science and Technology(No.2016YFB0401001)the State Key Laboratory of Advanced Technologies for Comprehensive Utilization of Platinum Metals
文摘Room-temperature phosphorescence（RTP） materials have attracted great attention due to their involvement of excited triplet states and comparatively long decay lifetimes.In this short review,recent progress on enhancement of RTP from purely organic materials is summarized.According to the mechanism of phosphorescence emission,two principles are discussed to construct efficient RTP materials：one is promoting intersystem crossing（ISC） efficiency by using aromatic carbonyl,heavyatom,or/and heterocycle/heteroatom containing compounds;the other is suppressing intramolecular motion and intermolecular collision which can quench excited triplet states,including embedding phosphors into polymers and packing them tightly in crystals.With aforementioned strategies,RTP from purely organic materials was achieved both in fluid and rigid media.
