Luminescent materials that can be reversibly switched by electric field stimulation are attractive since the potential application for optoelectronic devices.Here we report a triplet-triplet annihilation upconversion(...Luminescent materials that can be reversibly switched by electric field stimulation are attractive since the potential application for optoelectronic devices.Here we report a triplet-triplet annihilation upconversion(TTA-UC)system with electrophoretic response which is developed as the electrophoretic ink.The TTA-UC system consists of an ionic derivative of 9,10-diphenyl anthracene(DPA)as the annihilator and Pt(II)octaethylporphyrin(PtOEP)as the sensitizer.Upon applying an electric field,migration and enrichment of positively charged DPA derivatives towards the cathode results in a 20%enhancement of TTA-UC.A quasi-solid film for electrically writing is made using the electrophoretic TTA system as the ink and a platinum electrode as a pen.The prototype of TTA-UC ink demonstrates unique luminescence functions upon electrically writing and erasing,providing a promising strategy to develop electronic devices for display,information storage and encryption.展开更多
The enhancement in the efficiency of triplet-triplet annihilation upconversion(TTA-UC)is mainly determined by the triplet energy transfer(TET)and triplet-triplet annihilation(TTA)between the sensitizers and annihilato...The enhancement in the efficiency of triplet-triplet annihilation upconversion(TTA-UC)is mainly determined by the triplet energy transfer(TET)and triplet-triplet annihilation(TTA)between the sensitizers and annihilators.The TET process works efficiently by adjusting the concentration ratio of the sensitizers and annihilators.The efficiency of TTA is determined by the properties of the annihilator.Because TTA is a Dexter-type energy transfer and is affected by the diffusion rate,the energy levels of the excited states and the molecular size are both crucial in TTA.In this study,four isomerized dimers of 9,10-diphenlanthracene(DPA)and anthracene(An)were designed and prepared as annihilators for TTA-UC.The singlet and triplet energy levels could be adjusted by altering the connection position while maintaining the molecular weight and size.When PtOEP was used as the sensitizer,the maximum upconversion efficiency of 9-[4-(9-anthracenyl)phenyl]-10-phenylanthracene(9DPA-9An)was~11.18%.This is four times higher than that of 9,10-diphenyl-2,9-bianthracene(2DPA-9An,2.63%).The calculation of the energies of T_(1)and the higher triplet state(T_(3),because E(T_(2))is similar to the E(T)of these dimers)for these dimers has provided insights into the underlying reasons.These indicated that the energy gap value of 2×E(T_(1))-E(T_(3))is the determining factor for TTA efficiency.This work may provide a better understanding of the excited-state energy levels,which is crucial for designing novel annihilators to enhance the TTA-UCefficiency.展开更多
Photon upconversion is an anti-Stokes process that converts low-energy photons into high-energy photons.The use of upconversion luminescence can avoid the autofluorescence of biological tissue and realize background-f...Photon upconversion is an anti-Stokes process that converts low-energy photons into high-energy photons.The use of upconversion luminescence can avoid the autofluorescence of biological tissue and realize background-free bioimaging with a high signal-to-noise ratio at a low power density.In addition,the excitation of red or near-infrared light facilitates the reduction of photodamage in biological tissues and subsequent bioimaging of deep tissue features in vivo.Meanwhile,upconversion emission-mediated bio sensing offers both high sensitivity and low detection limits for quantitative analysis of the target substances in complicated biological samples.Due to its high upconversion quantum yield,low excitation power density,and tunable absorption and emission wavelengths,triplet-triplet annihilation upconversion(TTA-UC)has garnered considerable interest for bioimaging and biosensing.This review will introduce the fundamental concepts of TTA-UC,the factors that influence TTA-UC materials,and the methodologies for preparing TTA-UC materials.The important progress of TTA-UC in bioimaging and bio sensing in recent years will also be discussed in detail in vitro and in vivo.Furthermore,the current challenges of TTA-UC in bioimaging and biosensing will be discussed,along with potential solutions.展开更多
A derivative of fluorescein,fluorescein O,O-diacrylate(FODA),was utilized in a triplet-triplet annihilation upconversion(TTA-UC)system to develop a composite ratiometric chemosensor capable of detecting cysteine(Cys)....A derivative of fluorescein,fluorescein O,O-diacrylate(FODA),was utilized in a triplet-triplet annihilation upconversion(TTA-UC)system to develop a composite ratiometric chemosensor capable of detecting cysteine(Cys).FODA acted as both the probe for Cys and the energy acceptor for upconversion(UC)emission,thereby making UC a responsive signal to Cys.In addition,the phosphorescence signal of the sensitizer in the TTA-UC system remained constant and did not respond to Cys,making it an ideal internal reference signal for constructing a ratiometric sensor.Through this simple strategy,traditional fluorescent probes can be combined with TTA-UC system to establish a ratiometric sensing platform,which can be applied in more scenarios due to the longer wavelength excitation.展开更多
It has been challenging to develop deep blue organic molecular fluorescent emitters with CIE y(y≤0.08)based on triplet-triplet annihilation(TTA). Here, we report facilely available dianthracenylphenylenebased emitter...It has been challenging to develop deep blue organic molecular fluorescent emitters with CIE y(y≤0.08)based on triplet-triplet annihilation(TTA). Here, we report facilely available dianthracenylphenylenebased emitters, which have a 3,5-di(4-t-butylphenyl)phenyl moiety at the one end and 4-cyanophenyl or 3-pyridyl at the other end, respectively. Both fluorophores show a high glass transition temperature of over 220℃ with a thermal decomposition temperature of over 430℃ at an initial weight loss of1%. The preliminary characterizations of the organic light-emitting diodes(OLEDs) that utilized these nondoped emitters provided high EQEs of 4.6%à5.9% with CIE coordinates(0.15, 0.07–0.08). The analysis of the EL transient decay revealed that TTA contributed to the observed performance. The results show that the new emitters are attractive as a potential TTA-based host to afford stable deep blue fluorescent OLEDs.展开更多
Water-soluble triplet sensitizer with permethyl-β-cyclodextrin(PMCD)grafting on a Schiff-base Pt(II)complex(Pt-2),in which PMCD unit serves as a host for binding the acceptors and the Schiff-base Pt(II)complex serves...Water-soluble triplet sensitizer with permethyl-β-cyclodextrin(PMCD)grafting on a Schiff-base Pt(II)complex(Pt-2),in which PMCD unit serves as a host for binding the acceptors and the Schiff-base Pt(II)complex serves as a triplet sensitizer,was synthesized to investigate the effect of supramolecular complexation and assembly on the triplet-triplet annihilation upconversion emission in water.9,10-Diphenylanthracence(DPA)carboxylate(A-1)and its dimer(A-2)in which two DPA carboxylate were covalently linked with an alkyl chain were synthesized as triplet acceptors which also play a role of guest molecules for PMCD.A-1 and A-2 showed high affinity with PMCD,and A-2 can readily aggregate in water and form micron sized assemblies due to the hydrophobic effect andπ-πstacking of anthracene core in A-2.The efficiency of TTA-UC was demonstrated to be enhanced by a synergistic effect of host-guest complexation of Pt-2 with A-2 and the self-aggregation of the acceptor A-2,which facilitated the energy transfer and energy fusion among donor and acceptor.展开更多
3D direct-writing via photopolymerization based on two-photon absorption(TPA) can achieve excellent out-of-plane resolution.The key to this technology is a quadratic intensity dependence in photoexciting the TPA photo...3D direct-writing via photopolymerization based on two-photon absorption(TPA) can achieve excellent out-of-plane resolution.The key to this technology is a quadratic intensity dependence in photoexciting the TPA photosensitizers. Triplet-triplet annihilation(TTA) also has similar nonlinear light-intensity dependence. As a result, TTA can also generate spatially confined excitation near the beam focus. Combining the photopolymerization reaction with the TTA system composed of palladium porphyrin and diphenylanthracene, 3D direct-writing micro-fabrication based on photopolymerization and the TTAwas realized.The out-of-plane resolution can reach 10 μm under continuous-wave laser excitation. TTA-based 3D direct-writing technology does not need an expensive femtosecond pulsed laser, showing the potential of a next-generation 3D printing technology.展开更多
基金the financial support from the National Natural Science Foundation of China(Nos.22273117,22273110 and 22090012)。
文摘Luminescent materials that can be reversibly switched by electric field stimulation are attractive since the potential application for optoelectronic devices.Here we report a triplet-triplet annihilation upconversion(TTA-UC)system with electrophoretic response which is developed as the electrophoretic ink.The TTA-UC system consists of an ionic derivative of 9,10-diphenyl anthracene(DPA)as the annihilator and Pt(II)octaethylporphyrin(PtOEP)as the sensitizer.Upon applying an electric field,migration and enrichment of positively charged DPA derivatives towards the cathode results in a 20%enhancement of TTA-UC.A quasi-solid film for electrically writing is made using the electrophoretic TTA system as the ink and a platinum electrode as a pen.The prototype of TTA-UC ink demonstrates unique luminescence functions upon electrically writing and erasing,providing a promising strategy to develop electronic devices for display,information storage and encryption.
基金supported by the National Natural Science Foundation of China(22133006,21703287)the Natural Science Foundation of Shandong Province(ZR2023QB067,ZR2022MB065)+1 种基金the Science and Technology Program of the University of Jinan(XKY2068-140200568)Major Subject of the University of Jinan(1420702).
文摘The enhancement in the efficiency of triplet-triplet annihilation upconversion(TTA-UC)is mainly determined by the triplet energy transfer(TET)and triplet-triplet annihilation(TTA)between the sensitizers and annihilators.The TET process works efficiently by adjusting the concentration ratio of the sensitizers and annihilators.The efficiency of TTA is determined by the properties of the annihilator.Because TTA is a Dexter-type energy transfer and is affected by the diffusion rate,the energy levels of the excited states and the molecular size are both crucial in TTA.In this study,four isomerized dimers of 9,10-diphenlanthracene(DPA)and anthracene(An)were designed and prepared as annihilators for TTA-UC.The singlet and triplet energy levels could be adjusted by altering the connection position while maintaining the molecular weight and size.When PtOEP was used as the sensitizer,the maximum upconversion efficiency of 9-[4-(9-anthracenyl)phenyl]-10-phenylanthracene(9DPA-9An)was~11.18%.This is four times higher than that of 9,10-diphenyl-2,9-bianthracene(2DPA-9An,2.63%).The calculation of the energies of T_(1)and the higher triplet state(T_(3),because E(T_(2))is similar to the E(T)of these dimers)for these dimers has provided insights into the underlying reasons.These indicated that the energy gap value of 2×E(T_(1))-E(T_(3))is the determining factor for TTA efficiency.This work may provide a better understanding of the excited-state energy levels,which is crucial for designing novel annihilators to enhance the TTA-UCefficiency.
基金the financial support provided by Research start-up fund of Nankai UniversityTianjin Natural Science Foundation(S22QNG922)+1 种基金National Natural Science Fund for Excellent Young Scientists Fund Program(Overseas)(013398)the Open Fund of the State Key Laboratory of Fine Chemicals(Dalian University of Technology)(KF2111)
文摘Photon upconversion is an anti-Stokes process that converts low-energy photons into high-energy photons.The use of upconversion luminescence can avoid the autofluorescence of biological tissue and realize background-free bioimaging with a high signal-to-noise ratio at a low power density.In addition,the excitation of red or near-infrared light facilitates the reduction of photodamage in biological tissues and subsequent bioimaging of deep tissue features in vivo.Meanwhile,upconversion emission-mediated bio sensing offers both high sensitivity and low detection limits for quantitative analysis of the target substances in complicated biological samples.Due to its high upconversion quantum yield,low excitation power density,and tunable absorption and emission wavelengths,triplet-triplet annihilation upconversion(TTA-UC)has garnered considerable interest for bioimaging and biosensing.This review will introduce the fundamental concepts of TTA-UC,the factors that influence TTA-UC materials,and the methodologies for preparing TTA-UC materials.The important progress of TTA-UC in bioimaging and bio sensing in recent years will also be discussed in detail in vitro and in vivo.Furthermore,the current challenges of TTA-UC in bioimaging and biosensing will be discussed,along with potential solutions.
基金financially supported by National Natural Science Foundation of China(51873145)Qing Lan Project+1 种基金333 High-level Talents Training Project of Jiangsu Province(BRA2018340)Six Talent Summits Project of Jiangsu Province(XCL-79)
文摘A derivative of fluorescein,fluorescein O,O-diacrylate(FODA),was utilized in a triplet-triplet annihilation upconversion(TTA-UC)system to develop a composite ratiometric chemosensor capable of detecting cysteine(Cys).FODA acted as both the probe for Cys and the energy acceptor for upconversion(UC)emission,thereby making UC a responsive signal to Cys.In addition,the phosphorescence signal of the sensitizer in the TTA-UC system remained constant and did not respond to Cys,making it an ideal internal reference signal for constructing a ratiometric sensor.Through this simple strategy,traditional fluorescent probes can be combined with TTA-UC system to establish a ratiometric sensing platform,which can be applied in more scenarios due to the longer wavelength excitation.
基金supported by the National Key R&D Program of China(2016YFB0400701)NSFC-Guangdong Joint Program(U1801258 and U1301243)+2 种基金Department of Science and Technology of Guangdong Province(2017A050503002)Foundation of Guangzhou Science and Technology Project(201504010012)the support of Dongguan Major Special Project(2017215117010)
文摘It has been challenging to develop deep blue organic molecular fluorescent emitters with CIE y(y≤0.08)based on triplet-triplet annihilation(TTA). Here, we report facilely available dianthracenylphenylenebased emitters, which have a 3,5-di(4-t-butylphenyl)phenyl moiety at the one end and 4-cyanophenyl or 3-pyridyl at the other end, respectively. Both fluorophores show a high glass transition temperature of over 220℃ with a thermal decomposition temperature of over 430℃ at an initial weight loss of1%. The preliminary characterizations of the organic light-emitting diodes(OLEDs) that utilized these nondoped emitters provided high EQEs of 4.6%à5.9% with CIE coordinates(0.15, 0.07–0.08). The analysis of the EL transient decay revealed that TTA contributed to the observed performance. The results show that the new emitters are attractive as a potential TTA-based host to afford stable deep blue fluorescent OLEDs.
基金the financial support of the National Natural Science Foundation of China(Nos.21971169,21871194,21572142,21372165 and 21321061)National Key Research and Development Program of China(No.2017YFA0505903)Science & Technology Department of Sichuan Province(Nos.2019YJ0090,2019YJ0160,2017SZ0021)
文摘Water-soluble triplet sensitizer with permethyl-β-cyclodextrin(PMCD)grafting on a Schiff-base Pt(II)complex(Pt-2),in which PMCD unit serves as a host for binding the acceptors and the Schiff-base Pt(II)complex serves as a triplet sensitizer,was synthesized to investigate the effect of supramolecular complexation and assembly on the triplet-triplet annihilation upconversion emission in water.9,10-Diphenylanthracence(DPA)carboxylate(A-1)and its dimer(A-2)in which two DPA carboxylate were covalently linked with an alkyl chain were synthesized as triplet acceptors which also play a role of guest molecules for PMCD.A-1 and A-2 showed high affinity with PMCD,and A-2 can readily aggregate in water and form micron sized assemblies due to the hydrophobic effect andπ-πstacking of anthracene core in A-2.The efficiency of TTA-UC was demonstrated to be enhanced by a synergistic effect of host-guest complexation of Pt-2 with A-2 and the self-aggregation of the acceptor A-2,which facilitated the energy transfer and energy fusion among donor and acceptor.
基金supported by the National Key R&D Program of China (2021YFA1502500)the National Natural Science Foundation of China (22125502 and 22071207)。
文摘3D direct-writing via photopolymerization based on two-photon absorption(TPA) can achieve excellent out-of-plane resolution.The key to this technology is a quadratic intensity dependence in photoexciting the TPA photosensitizers. Triplet-triplet annihilation(TTA) also has similar nonlinear light-intensity dependence. As a result, TTA can also generate spatially confined excitation near the beam focus. Combining the photopolymerization reaction with the TTA system composed of palladium porphyrin and diphenylanthracene, 3D direct-writing micro-fabrication based on photopolymerization and the TTAwas realized.The out-of-plane resolution can reach 10 μm under continuous-wave laser excitation. TTA-based 3D direct-writing technology does not need an expensive femtosecond pulsed laser, showing the potential of a next-generation 3D printing technology.
