Three lanthanide ions and a rigid(1,1'-biphenyl)-2,4,6-tricarboxylic acid(H_(3)bptc) ligand led to the isostructural lanthanide metal-organic frameworks(Ln-MOFs) {[Ln(bptc)(H_(2)O)_(3)]·3H_(2)O}_n(Lnbptc, Ln ...Three lanthanide ions and a rigid(1,1'-biphenyl)-2,4,6-tricarboxylic acid(H_(3)bptc) ligand led to the isostructural lanthanide metal-organic frameworks(Ln-MOFs) {[Ln(bptc)(H_(2)O)_(3)]·3H_(2)O}_n(Lnbptc, Ln = Eu,Tb, Gd, Eu_(x)Tb_(1—x), Eu_(x)Gd_(1-x), Tb_(x)Gd_(1-x), and Eu_(0.12)Tb_(0.52)Gd_(0.36)). The density functional theory(DFT) and time-dependent DFT calculation were expanded on H_3bptc, which point to the occurrence of “antenna effect”. The minor diameter samples of Eubptc, Tbbptc, and Gdbptc can also be attained via the microwave synthesis and employed for handwriting anticounterfeiting. Interestingly, the typical red emission of Eu^(3+) and green emission of Tb~(3+) could be fine-tuned by Gd^(3+) via chemical mixing to be full-color emissions bimetallic doped Eu_(x)Tb_(1-x)bptc, Eu_(x)Gd_(1-x)bptc, and Tb_(x)Gd_(1-x)bptc. The above synthetic bimetallic MOFs can be fixed in positioning boxes of quick response(QR) codes with diverse emission for anticounterfeiting. The message can be decoded under the irradiation of 365 nm ultraviolet lamp while invisible in the daylight. Notably, the trimetallic doped Eu_(0.12)Tb_(0.52)Gd_(0.36)bptc emits white light with the CIE color coordinate(0.34, 0.34). Furthermore, Tbbptc is demonstrated to be a sensitive probe toward nitrobenzene and acetone with multiple mechanisms.展开更多
Carbon dots(CDs)with room-temperature phosphorescence(RTP)have attracted dramatically growing interest in optical functional materials.However,the photoluminescence mechanism of CDs is still a vital and challenging to...Carbon dots(CDs)with room-temperature phosphorescence(RTP)have attracted dramatically growing interest in optical functional materials.However,the photoluminescence mechanism of CDs is still a vital and challenging topic.In this work,we prepared CD-based RTP materials via melting boric acid with various lengths of alkyl amine compounds as precursors.The spatial effect on the structure and the RTP properties of CDs were systematically investigated.With the increase in carbon chain length,the interplanar spacing of the carbon core expands and crosslink-enhanced emission weakens,resulting in a decrease in the phosphorescence intensity and lifetimes.Meanwhile,based on triplet-to-singlet resonance energy transfer,we employed intense and long-lived phosphorescence CDs as the donor and short-lived fluorescent dyes as the acceptor to achieve long-lived multicolor afterglow.By the triplet-to-singlet resonance energy transfer,the afterglow color can change from green to orange.The afterglow lifetimes are more than 0.9 s.Thanks to the outstanding afterglow properties,the composites were used for timeresolved and multiple-color advanced anticounterfeiting.This work will promote the design of multicolor and long-lived afterglow materials and expand their applications.展开更多
Counterfeiting-related crimes pose a serious threat to the economic interests,security,and health of governments,businesses,and consumers.The urgent need for advanced anticounterfeiting materials with multilevel secur...Counterfeiting-related crimes pose a serious threat to the economic interests,security,and health of governments,businesses,and consumers.The urgent need for advanced anticounterfeiting materials with multilevel security for information encryption and decryption has driven significant research in this area.Supramolecular luminescent materials are potential for anticounterfeiting owing to their dynamic and controllable optical properties.In this review,the strategies adopted for fabricating supramolecular fluorescent materials and their corresponding anticounterfeiting technologies have been discussed.Especially,the time-dependent luminescent materials,which were created by non-equilibrium supramolecular assemblies and exhibited significant changes in fluorescence intensity and wavelength over time,were highlighted for their unique dynamic feature.This feature endowed materials programmable properties on time dimension,allowing for automatic and spontaneous behavior.Consequently,a series of information encryption materials have been developed,including self-erasing fluorescence hydrogels and 4D codes,demonstrating an enhanced level of security.展开更多
Highly sensitive stimuli-responsive luminescent materials are crucial for appli-cations in optical sensing,security,and anticounterfeiting.Here,we report two zero-dimensional(0D)copper(I)halides,(TEP)_(2)Cu_(2)Br_(4),...Highly sensitive stimuli-responsive luminescent materials are crucial for appli-cations in optical sensing,security,and anticounterfeiting.Here,we report two zero-dimensional(0D)copper(I)halides,(TEP)_(2)Cu_(2)Br_(4),(TEP)_(2)Cu_(4)Br_(6),and 1D(TEP)_(3)Ag_(6)Br_(9),which are comprised of isolated[Cu_(2)Br_(4)]^(2-),[Cu_(4)Br_(6)]^(2-),and[Ag_(6)Br_(9)]3-polyanions,respectively,separated by TEP^(+)(tetraethylphosphonium[TEP])cations.(TEP)_(2)Cu_(2)Br_(4) and(TEP)_(2)Cu_(4)Br_(6) demonstrate greenish-white and orange-red emissions,respectively,with near unity photoluminescence quantum yields,while(TEP)_(3)Ag_(6)Br_(9) is a poor light emitter.Optical spectroscopy mea-surements and density-functional theory calculations reveal that photoemissions of these compounds originate from self-trapped excitons due to the excited-state distor-tions in the copper(I)halide units.Crystals of Cu(I)halides are radioluminescence active at room temperature under both X-andγ-rays exposure.The light yields up to 15,800 ph/MeV under 662 keVγ-rays of ^(137)Cs suggesting their potential for scintillation applications.Remarkably,(TEP)_(2)Cu_(2)Br_(4) and(TEP)_(2)Cu_(4)Br_(6) are inter-convertible through chemical stimuli or reverse crystallization.In addition,both compounds demonstrate luminescence on-off switching upon thermal stimuli.The sensitivity of(TEP)_(2)Cu_(2)Br_(4) and(TEP)_(2)Cu_(4)Br_(6) to the chemical and thermal stimuli coupled with their ultrabright emission allows their consideration for applications such as solid-state lighting,sensing,information storage,and anticounterfeiting.展开更多
The tunable excitation patterns and emission modes associated with luminescence materials,such as downshifting luminescence(DSL),upconversion luminescence(UCL),and mechanoluminescence(ML)play an important role in info...The tunable excitation patterns and emission modes associated with luminescence materials,such as downshifting luminescence(DSL),upconversion luminescence(UCL),and mechanoluminescence(ML)play an important role in information encryption and anticounterfeiting.However,many reported luminescence materials usually show fixed excitation patterns and unimodal output,resulting in a low anticounterfeiting level.Therefore,developing luminescence materials with multitemporal,variation excitation patterns and multiple emission modes remains a considerable challenge,particularly in a single matrix.This study reports a highly integrated multifunctional material(color-tunable(DSL:amaranth→blue),tunable excitation patterns(250±380 nm)and quadrimodal(DSL,UCL,persistent luminescence(PersL),and ML)).The as-obtained versatile LaCaAl_(3)O_(7):Eu^(2+)/^(3+),Yb^(3+),Er^(3+)materials are suitable for obtaining elastomer films with the characteristics of water resistance,stretchability,and flexibility and synchronously offer multidimensional information encryptions and anticounterfeiting using common tools(ultraviolet light,nearinfrared light,and pen).These results provide a unique insight into advanced multimodal anticounterfeiting.展开更多
Multimodal anticounterfeiting has become increasingly challenging in modern society to guarantee information security and the safety of property.In this study,a versatile cholesterol-containing tetraphenylethene deriv...Multimodal anticounterfeiting has become increasingly challenging in modern society to guarantee information security and the safety of property.In this study,a versatile cholesterol-containing tetraphenylethene derivative is shown to have multiple optical properties,including stimuli-responsive fluorescence,reversible photochromism,excitation wavelength dependent luminescence,and circularly polarized luminescence.After the application of diverse processing methods(writing,screen painting,drawing,and pyrography),we found that this molecule can serve as an anticounterfeiting toolbox to provide rich anticounterfeiting effects through the synergistical use of multiple optical properties.This work offers important insight for designing novel small organic molecules for advanced multimodal anticounterfeiting technology.展开更多
The second near-infrared window in a 1500-1700 nm region(known as the NIR-IIb region)presents low autofluorescence and a deep penetration depth,enabling a potential technology for effective imaging and anticounterfeit...The second near-infrared window in a 1500-1700 nm region(known as the NIR-IIb region)presents low autofluorescence and a deep penetration depth,enabling a potential technology for effective imaging and anticounterfeiting applications.However,existing NIR-IIb-emitted fluorescence materials remain limited and possess low luminescent properties.In implementing the enhanced~1525 nm emission of the Er(III)complex in a nonorganic solvent,an amphiphilic diblock copolymer(PEG112-PAA12)was initially synthesized to coordinate with Er(III),and then certain Yb(III)was doped to form the PEG-PAA-Er/Yb complex.The complex shows a dramatic fluorescent enhancement of~250-fold at~1525 nm in D_(2)O than that in H_(2)O under 980-nm laser irradiation,which is ascribed to the following factors:(1)The substitution of H_(2)O by D_(2)O can suppress the quenching effect of H_(2)O at~1470 nm to achieve the emission of PEG-PAA-Er;(2)the doping of Yb(III)enables the co-luminescence effect to PEG-PAA-Er to improve NIR-IIb emission.Notably,the PEG-PAA-Er/Yb complex can construct molecular logic gates with logic functions and optical anticounterfeiting by using the abovementioned fluorescence changes.展开更多
基金Project supported by the National Natural Science Foundation of China(22071194,21971207)。
文摘Three lanthanide ions and a rigid(1,1'-biphenyl)-2,4,6-tricarboxylic acid(H_(3)bptc) ligand led to the isostructural lanthanide metal-organic frameworks(Ln-MOFs) {[Ln(bptc)(H_(2)O)_(3)]·3H_(2)O}_n(Lnbptc, Ln = Eu,Tb, Gd, Eu_(x)Tb_(1—x), Eu_(x)Gd_(1-x), Tb_(x)Gd_(1-x), and Eu_(0.12)Tb_(0.52)Gd_(0.36)). The density functional theory(DFT) and time-dependent DFT calculation were expanded on H_3bptc, which point to the occurrence of “antenna effect”. The minor diameter samples of Eubptc, Tbbptc, and Gdbptc can also be attained via the microwave synthesis and employed for handwriting anticounterfeiting. Interestingly, the typical red emission of Eu^(3+) and green emission of Tb~(3+) could be fine-tuned by Gd^(3+) via chemical mixing to be full-color emissions bimetallic doped Eu_(x)Tb_(1-x)bptc, Eu_(x)Gd_(1-x)bptc, and Tb_(x)Gd_(1-x)bptc. The above synthetic bimetallic MOFs can be fixed in positioning boxes of quick response(QR) codes with diverse emission for anticounterfeiting. The message can be decoded under the irradiation of 365 nm ultraviolet lamp while invisible in the daylight. Notably, the trimetallic doped Eu_(0.12)Tb_(0.52)Gd_(0.36)bptc emits white light with the CIE color coordinate(0.34, 0.34). Furthermore, Tbbptc is demonstrated to be a sensitive probe toward nitrobenzene and acetone with multiple mechanisms.
基金The authors greatly acknowledge the Natural Science Foundation of Jiangsu Province(No.BK20220351)Natural Science Foundation of the Jiangsu Higher Education Institutions of China(No.22KJB150027)for financial support.
文摘Carbon dots(CDs)with room-temperature phosphorescence(RTP)have attracted dramatically growing interest in optical functional materials.However,the photoluminescence mechanism of CDs is still a vital and challenging topic.In this work,we prepared CD-based RTP materials via melting boric acid with various lengths of alkyl amine compounds as precursors.The spatial effect on the structure and the RTP properties of CDs were systematically investigated.With the increase in carbon chain length,the interplanar spacing of the carbon core expands and crosslink-enhanced emission weakens,resulting in a decrease in the phosphorescence intensity and lifetimes.Meanwhile,based on triplet-to-singlet resonance energy transfer,we employed intense and long-lived phosphorescence CDs as the donor and short-lived fluorescent dyes as the acceptor to achieve long-lived multicolor afterglow.By the triplet-to-singlet resonance energy transfer,the afterglow color can change from green to orange.The afterglow lifetimes are more than 0.9 s.Thanks to the outstanding afterglow properties,the composites were used for timeresolved and multiple-color advanced anticounterfeiting.This work will promote the design of multicolor and long-lived afterglow materials and expand their applications.
基金supported by the National Natural Science Foundation of China(22025503,22220102004,and 22401093)the Science and Technology Commission of Shanghai Municipality(24DX1400200)+2 种基金the Innovation Program of Shanghai Municipal Education Commission(2023ZKZD40)the Programme of Introducing Talents of Discipline to Universities(B16017)the Fundamental Research Funds for the Central Universities,and the China Postdoctoral Science Foundation(2023M741167 and GZB20230211)。
文摘Counterfeiting-related crimes pose a serious threat to the economic interests,security,and health of governments,businesses,and consumers.The urgent need for advanced anticounterfeiting materials with multilevel security for information encryption and decryption has driven significant research in this area.Supramolecular luminescent materials are potential for anticounterfeiting owing to their dynamic and controllable optical properties.In this review,the strategies adopted for fabricating supramolecular fluorescent materials and their corresponding anticounterfeiting technologies have been discussed.Especially,the time-dependent luminescent materials,which were created by non-equilibrium supramolecular assemblies and exhibited significant changes in fluorescence intensity and wavelength over time,were highlighted for their unique dynamic feature.This feature endowed materials programmable properties on time dimension,allowing for automatic and spontaneous behavior.Consequently,a series of information encryption materials have been developed,including self-erasing fluorescence hydrogels and 4D codes,demonstrating an enhanced level of security.
文摘Highly sensitive stimuli-responsive luminescent materials are crucial for appli-cations in optical sensing,security,and anticounterfeiting.Here,we report two zero-dimensional(0D)copper(I)halides,(TEP)_(2)Cu_(2)Br_(4),(TEP)_(2)Cu_(4)Br_(6),and 1D(TEP)_(3)Ag_(6)Br_(9),which are comprised of isolated[Cu_(2)Br_(4)]^(2-),[Cu_(4)Br_(6)]^(2-),and[Ag_(6)Br_(9)]3-polyanions,respectively,separated by TEP^(+)(tetraethylphosphonium[TEP])cations.(TEP)_(2)Cu_(2)Br_(4) and(TEP)_(2)Cu_(4)Br_(6) demonstrate greenish-white and orange-red emissions,respectively,with near unity photoluminescence quantum yields,while(TEP)_(3)Ag_(6)Br_(9) is a poor light emitter.Optical spectroscopy mea-surements and density-functional theory calculations reveal that photoemissions of these compounds originate from self-trapped excitons due to the excited-state distor-tions in the copper(I)halide units.Crystals of Cu(I)halides are radioluminescence active at room temperature under both X-andγ-rays exposure.The light yields up to 15,800 ph/MeV under 662 keVγ-rays of ^(137)Cs suggesting their potential for scintillation applications.Remarkably,(TEP)_(2)Cu_(2)Br_(4) and(TEP)_(2)Cu_(4)Br_(6) are inter-convertible through chemical stimuli or reverse crystallization.In addition,both compounds demonstrate luminescence on-off switching upon thermal stimuli.The sensitivity of(TEP)_(2)Cu_(2)Br_(4) and(TEP)_(2)Cu_(4)Br_(6) to the chemical and thermal stimuli coupled with their ultrabright emission allows their consideration for applications such as solid-state lighting,sensing,information storage,and anticounterfeiting.
基金supported by the National Natural Science Foundation of China(21871122 and 21431002)the Fundamental Research Funds for the Central Universities(lzujbky-2021-kb17)。
文摘The tunable excitation patterns and emission modes associated with luminescence materials,such as downshifting luminescence(DSL),upconversion luminescence(UCL),and mechanoluminescence(ML)play an important role in information encryption and anticounterfeiting.However,many reported luminescence materials usually show fixed excitation patterns and unimodal output,resulting in a low anticounterfeiting level.Therefore,developing luminescence materials with multitemporal,variation excitation patterns and multiple emission modes remains a considerable challenge,particularly in a single matrix.This study reports a highly integrated multifunctional material(color-tunable(DSL:amaranth→blue),tunable excitation patterns(250±380 nm)and quadrimodal(DSL,UCL,persistent luminescence(PersL),and ML)).The as-obtained versatile LaCaAl_(3)O_(7):Eu^(2+)/^(3+),Yb^(3+),Er^(3+)materials are suitable for obtaining elastomer films with the characteristics of water resistance,stretchability,and flexibility and synchronously offer multidimensional information encryptions and anticounterfeiting using common tools(ultraviolet light,nearinfrared light,and pen).These results provide a unique insight into advanced multimodal anticounterfeiting.
基金This work was supported by the National Natural Science Foundation of China(grant no.21905177)the Natural Science Foundation of Guangdong Province(grant nos.2019KZDXM008 and 2021A1515010192)the Fundamental Foundation of Shenzhen(grant no.JCYJ20210324094607021).
文摘Multimodal anticounterfeiting has become increasingly challenging in modern society to guarantee information security and the safety of property.In this study,a versatile cholesterol-containing tetraphenylethene derivative is shown to have multiple optical properties,including stimuli-responsive fluorescence,reversible photochromism,excitation wavelength dependent luminescence,and circularly polarized luminescence.After the application of diverse processing methods(writing,screen painting,drawing,and pyrography),we found that this molecule can serve as an anticounterfeiting toolbox to provide rich anticounterfeiting effects through the synergistical use of multiple optical properties.This work offers important insight for designing novel small organic molecules for advanced multimodal anticounterfeiting technology.
基金supported by the National Natural Science Foundation of China(Nos.22104056,62288102,and 82302356)Natural Science Foundation of Jiangsu Province(No.BK20210176)+3 种基金2021 JiangSu Shuangchuang(Mass Innovation and Entrepreneurship)Talent Program(No.JSSCBS20210040)the Open Research Fund of State Key Laboratory of Digital Medical Engineering of Southeast University(No.5507059002)the Natural Science Foundation of Fujian Province(No.2023J01529)the innovation team of photoelectric functional materials and devices for biomedical theranostics of Fujian Normal University(No.Y07204080K13).
文摘The second near-infrared window in a 1500-1700 nm region(known as the NIR-IIb region)presents low autofluorescence and a deep penetration depth,enabling a potential technology for effective imaging and anticounterfeiting applications.However,existing NIR-IIb-emitted fluorescence materials remain limited and possess low luminescent properties.In implementing the enhanced~1525 nm emission of the Er(III)complex in a nonorganic solvent,an amphiphilic diblock copolymer(PEG112-PAA12)was initially synthesized to coordinate with Er(III),and then certain Yb(III)was doped to form the PEG-PAA-Er/Yb complex.The complex shows a dramatic fluorescent enhancement of~250-fold at~1525 nm in D_(2)O than that in H_(2)O under 980-nm laser irradiation,which is ascribed to the following factors:(1)The substitution of H_(2)O by D_(2)O can suppress the quenching effect of H_(2)O at~1470 nm to achieve the emission of PEG-PAA-Er;(2)the doping of Yb(III)enables the co-luminescence effect to PEG-PAA-Er to improve NIR-IIb emission.Notably,the PEG-PAA-Er/Yb complex can construct molecular logic gates with logic functions and optical anticounterfeiting by using the abovementioned fluorescence changes.
基金financial support from the National Natural Science Foundation of China(22078238,21961132005,and 21908160)the National Key Research and Development Program of China(2022YFC2104800 and 2021YFC2100800).
