Molecular engineering is a crucial strategy for improving the photovoltaic performance of dye-sensitized solar cells(DSSCs). Despite the common use of the donor-π bridge-acceptor architecture in designing sensitizers...Molecular engineering is a crucial strategy for improving the photovoltaic performance of dye-sensitized solar cells(DSSCs). Despite the common use of the donor-π bridge-acceptor architecture in designing sensitizers, the underlying structure-performance relationship remains not fully understood. In this study, we synthesized and characterized three sensitizers: MOTP-Pyc, MOS_(2)P-Pyc, and MOTS_(2)P-Pyc, all featuring a bipyrimidine acceptor. Absorption spectra, cyclic voltammetry, and transient photoluminescence spectra reveal a photo-induced electron transfer(PET) process in the excited sensitizers. Electron spin resonance spectroscopy confirmed the presence of charge-separated states. The varying donor and π-bridge structures among the three sensitizers led to differences in their conjugation effect, influencing light absorption abilities and PET processes and ultimately impacting the photovoltaic performance. Among the synthesized sensitizers, MOTP-Pyc demonstrated a DSSC efficiency of 3.04%. Introducing an additional thienothiophene block into the π-bridge improved the DSSC efficiency to 4.47% for MOTS_(2)P-Pyc. Conversely, replacing the phenyl group with a thienothiophene block reduced DSSC efficiency to 2.14% for MOS_(2)P-Pyc. Given the proton-accepting ability of the bipyrimidine module, we treated the dye-sensitized TiO_(2) photoanodes with hydroiodic acid(HI), significantly broadening the light absorption range. This treatment greatly enhanced the short-circuit current density of DSSCs owing to the enhanced electron-withdrawing ability of the acceptor. Consequently, the HI-treated MOTS_(2)P-Pyc-based DSSCs achieved the highest power conversion efficiency of 7.12%, comparable to that of the N719 dye at 7.09%. This work reveals the positive role of bipyrimidine in the design of organic sensitizers for DSSC applications.展开更多
The stable coordinated metallo-complexes based on 2,2′:6′,2″-terpyridine(tpy)and its derivatives have been widely researched for various wide-ranging applications in photoelectronics,catalysis,sensor,photoluminesce...The stable coordinated metallo-complexes based on 2,2′:6′,2″-terpyridine(tpy)and its derivatives have been widely researched for various wide-ranging applications in photoelectronics,catalysis,sensor,photoluminescence,and so on.However,the most reported studies ignored the comprehensive comparison between structures modified by different positions and photoluminescence.Herein,we design a series of metallo-complexes which were assembled with tpy substituted triphenylamine(TPA)at different positions and metal ions and explored their photophysical properties.In the solution state,MLE_(2)based on the 5,5″-positions modification showed the highest PLQYs and PL intensity.With the increase of solvent polarity,MLB2exhibit the largest redshift.In the solid state,from MLA_(2)to MLE_(2),the emission colours are gradually red-shifted from yellow to red.The findings in this work may pave a new way to design functional metallo-complexes,not just for PL properties.展开更多
Precision medicine calls for advanced theranostics that integrate controllable diagnostic and therapeutic capabilities into one platform for disease treatment in the early stage.Phototheranostics such as fluorescence ...Precision medicine calls for advanced theranostics that integrate controllable diagnostic and therapeutic capabilities into one platform for disease treatment in the early stage.Phototheranostics such as fluorescence imaging(FLI),photoacoustic imaging(PAI),photodynamic therapy(PDT),and photothermal therapy(PTT)have attracted considerable attention in recent years,which mainly employ different excited-state energy dissipation pathways of a chromophore.According to the Jablonski diagram,FLI is related to the radiative process,PAI and PTT are derived from the nonradiative thermal deactivation,and PDT originates from the triplet state energy,in which these processes are usually competitive.Therefore,it is critically important to precisely tune the photophysical energy transformation processes to realize certain diagnosis and treatment properties in optimal state for boosting biomedical applications.Currently,there are mainly two strategies including chemical structure and aggregate behavior changes that relate to the regulation of excited state energy dissipation.In this review,we will discuss the recent advances of smart molecular probes that the photophysical properties can be regulated by external triggers and their applications in biomedical fields.We will summarize the development of activatable phototheranostic molecular probes in response to stimuli such as reactive oxygen species,pH,light,hypoxia,enzyme and gas.The assembly and disassembly of molecular aggregates that greatly affect the photophysical energy transformation processes will also be highlighted.This review aims to provide valuable insights into the development of more accurate diagnostic and therapeutic systems,thereby advancing the emerging field of smart medicine.展开更多
Synthesis, IR spectra, UV vis spectra and photophysical properties of Gd 3+ , Eu 3+ , Tb 3+ complexes with 3,4 furandicarboxylic acid and 1,10 phenanthroline are reported. Intramolecular energy transfe...Synthesis, IR spectra, UV vis spectra and photophysical properties of Gd 3+ , Eu 3+ , Tb 3+ complexes with 3,4 furandicarboxylic acid and 1,10 phenanthroline are reported. Intramolecular energy transfer process for these complexes is discussed in detail. It is found that the intramolecular energy transfer efficiency depends on the relative positions between the resonance energy levels of the central rare earth ions and the lowest triplet state energies of ligands.展开更多
The polymeric ligand PBIa （functionalized polybenzimidazole containing β-diketone side group） was successfully synthesized via the reaction of polybenzimidazole （PBI） with 3-Br-acetylacetone in DM SO solvent usin...The polymeric ligand PBIa （functionalized polybenzimidazole containing β-diketone side group） was successfully synthesized via the reaction of polybenzimidazole （PBI） with 3-Br-acetylacetone in DM SO solvent using Nail as the deprotonation reagent. Its corresponding polymeric complexes of Dy^3＋ and Gd^3＋ were prepared and characterized by FT-IR, ^1H NMR, molar conductance measurements, and thermal analysis. The photoluminescence properties and the probable mechanism of the Dy and Gd complexes were studied. The measurement and analysis of the thermal properties showed that these were thermal stable.展开更多
A novel anthraquinone phthalocyanine AI（Ⅲ） 4 and Co（Ⅱ） 5 were synthesized and characterized by elemental analysis, IR UV/ vis, ^1H NMlL HPLC and MS. The photophysical properties of the two metal complexes were s...A novel anthraquinone phthalocyanine AI（Ⅲ） 4 and Co（Ⅱ） 5 were synthesized and characterized by elemental analysis, IR UV/ vis, ^1H NMlL HPLC and MS. The photophysical properties of the two metal complexes were studied and compared by fluorescence spectrum method.展开更多
The composition ratio of donor and acceptor materials in organic bulk heterojunction (BHJ) is one of the key parameters to govern the performance in organic solar cells (OSCs). Therefore, high-performance non-fulleren...The composition ratio of donor and acceptor materials in organic bulk heterojunction (BHJ) is one of the key parameters to govern the performance in organic solar cells (OSCs). Therefore, high-performance non-fullerene organic bulk heterojunction consisting of poly[(2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b' ]dithiophene))-co-(1,3-di(5-thiophene-2-yl)–5,7-bis(2-ethylhexyl) benzo[1,2-c:4,5-c']dithiophene-4,8-dione)] (PBDB-T) and 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))–5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2' ,3'-d' ]-s-indaceno[1,2-b:5,6-b' ]-dithio-phene (ITIC) are used to investigate the correlation among various donor: acceptor (D:A) ratios, photophysical properties and photovoltaic performance. Interestingly, the function of short-circuit current (Jsc) and D:A ratios demonstrates an axisymmetric trend. When the blending ratio of D:A deviates from the optimal ratio, the symmetrically decreased Jsc is derived from a reduction in the D:A interface or amorphous region. Research on the steady-state photoluminescence (PL), the time-resolved fluorescence spectroscopy measurements, atomic force microscopic (AFM) and grazing-incidence small angle X-rays scattering (GIWAXS) indicates no significant variation in energy loss in the process of changing D:A ratios in BHJs. With high donor or acceptor content, the domain size improves significantly, but the distance of π-π stacking corresponding to molecular packing has not changed significantly, and the bi-continuous percolation pathways were not obviously influenced.展开更多
One ternary complex of europium with the plant growth regulator HDPHA (2-Hydroxydiphenyl acetic acid) and Phen (1,10-Phenanthroline), Eu(DPHA) 3·Phen·2H 2O, was synthesized and characterized by the element...One ternary complex of europium with the plant growth regulator HDPHA (2-Hydroxydiphenyl acetic acid) and Phen (1,10-Phenanthroline), Eu(DPHA) 3·Phen·2H 2O, was synthesized and characterized by the elemental analysis and DTA-TG measurement. The photophysical property of the complex was investigated by means of IR spectra, Raman spectrum and laser-exited, high-resolved excitation and emission spectra as well as time-resolved luminescence spectra. The luminescence spectra reveal four Eu 3+ sites with energy difference within 25 cm -1 and local symmetries of C 1 or C 2 or C s in the complex. The energy transfer among the Eu 3+ sites is observed. The 7F J sublevel splitting of the Eu 3+ ion is discussed.展开更多
A novel octupolar chromophore with 1,3,5-triazine as core,2,7-divinylene-9,9-dimethylfluorene as extendedπ-conjugated bridge,triarylamine as the electron-donating end-groups was successfully synthesized and character...A novel octupolar chromophore with 1,3,5-triazine as core,2,7-divinylene-9,9-dimethylfluorene as extendedπ-conjugated bridge,triarylamine as the electron-donating end-groups was successfully synthesized and characterized.Their linear photophysical and two-photon absorption（TPA） properties were investigated by UV absorption,excited fluorescence（SPEF） spectra and nonlinear transmission method,respectively.The absorption cut-off of the chromophore is below 520 nm and it has stronger fluorescence emission in a nonpolar solvent.In addition,the chromophore exhibits larger TPA cross-section（226.0 GM） in the femtosecond regime at 800 nm.展开更多
A series of linear and V-shaped oligo(phenylene ethynylene) derivatives 1-3 were synthesized through sequent Sonogashira coupling and propargyl alcohol deprotection reaction in high yields.The alkoxy chains(i.e.,n-hex...A series of linear and V-shaped oligo(phenylene ethynylene) derivatives 1-3 were synthesized through sequent Sonogashira coupling and propargyl alcohol deprotection reaction in high yields.The alkoxy chains(i.e.,n-hexyloxy groups) were introduced to assure good solubility of compounds 1-3 in common solvents.The photophysical properties of 1-3 in solution depend strongly on the geometries of these compounds.展开更多
Excited-state intramolecular proton transfer(ESIPT)is favored by researchers because of its unique optical properties.However,there are relatively few systematic studies on the effects of changing the electronegativit...Excited-state intramolecular proton transfer(ESIPT)is favored by researchers because of its unique optical properties.However,there are relatively few systematic studies on the effects of changing the electronegativity of atoms on the ESIPT process and photophysical properties.Therefore,we selected a series of benzoxazole isothiocyanate fluorescent dyes(2-HOB,2-HSB,and 2-HSe B)by theoretical methods,and systematically studied the ESIPT process and photophysical properties by changing the electronegativity of chalcogen atoms.The calculated bond angle,bond length,energy gap,and infrared spectrum analysis show that the order of the strength of intramolecular hydrogen bonding of the three molecules is 2-HOB<2-HSB<2-HSe B.Correspondingly,the magnitude of the energy barrier of the potential energy curve is 2-HOB>2-HSB>2-HSe B.In addition,the calculated electronic spectrum shows that as the atomic electronegativity decreases,the emission spectrum has a redshift.Therefore,this work will offer certain theoretical guidance for the synthesis and application of new dyes based on ESIPT properties.展开更多
A new 2-chloro-5,10,15-tris（2,4,6-triphenylphenyl）-corrole was accidentally synthesized in an acceptable yield of 5.7% during the synthesis of its parent corrole, in which DDQ served as oxidant and chlorinating agen...A new 2-chloro-5,10,15-tris（2,4,6-triphenylphenyl）-corrole was accidentally synthesized in an acceptable yield of 5.7% during the synthesis of its parent corrole, in which DDQ served as oxidant and chlorinating agent. The compound was well characterized by X-ray diffraction analysis,;H NMR, mass spectroscopy and absorption spectroscopy. Photophysical properties tests revealed that the chlorination caused a sharp decrease in fluorescence intensity, fluorescence life time, and fluorescence quantum yield.Electrochemical investigation demonstrated the positive shift of redox potentials for chlorinated corrole as compared to non-chlorinated corrole.展开更多
A diquinoxalinopyrene （DQP） derivative and the corresponding oligomers （PDQPs） with Mn of ca. 3300, 4200, 5600, and 7300 have been synthesized. It is found that the band gaps and highest occupied molecular orbital...A diquinoxalinopyrene （DQP） derivative and the corresponding oligomers （PDQPs） with Mn of ca. 3300, 4200, 5600, and 7300 have been synthesized. It is found that the band gaps and highest occupied molecular orbital （HOMO）/lowest unoccupied molecular orbital （LUMO） levels between DQP and its homopolymers only have a slight difference, implying a limited conjugation extension achieved from unimer to heptamer. The DFT calculation is in accordance with the experimental results. It reveals that the nodal planes are across the 2,11-positions in the LUMO and/or HOMO of DQP, dimer and trimer, which can be used to explain this special phenomenon.展开更多
The porphyrin-like macrocycles and their metal complexes are s novel family of photoresponsive molecules.The properties of the excited states,both singlet and triplet are investigated by the stationary and transient p...The porphyrin-like macrocycles and their metal complexes are s novel family of photoresponsive molecules.The properties of the excited states,both singlet and triplet are investigated by the stationary and transient processes.展开更多
A new type of anthracene crown ether 1, 8-anthraceno-18-crown-5 has been synthesizedand the photophysical properties upon complexation with alkali and alkaline-earth metal canonswere investigated. The fiuorescence qua...A new type of anthracene crown ether 1, 8-anthraceno-18-crown-5 has been synthesizedand the photophysical properties upon complexation with alkali and alkaline-earth metal canonswere investigated. The fiuorescence quantum yield and lifetime are appreciably enhanced, and thestability constant Ks were determined by fluorometric titration. It was found that the magnitude ofKs is controlled by the size and charge density of the complexed canons.展开更多
The photophysical behaviors of the oligomer based on 1,1'-binaphthol with3,3'-acetylene spacer were investigated. The oligomer molecule has a naphthyl-acetylene-naphthyl effective conjugation segment. The atro...The photophysical behaviors of the oligomer based on 1,1'-binaphthol with3,3'-acetylene spacer were investigated. The oligomer molecule has a naphthyl-acetylene-naphthyl effective conjugation segment. The atropic of the 1,1'-binaphthyl moiety led totwisted and rigid main chain in the oligomer. With the changes of the external environ-ment such as solvents used, solvent viscosity and ambient temperature, the wavelengthsof absorption and the intensities of fluorescence and absorption are changed slightly, butthe fluorescent intensity and quantum yield can be influenced. The luminescent behav-iors of the oligomer exhibit twisted intramolecular charge transfer characteristics, whichcould have a potential application in wavelength-stable light emitting material adaptableto ambient temperature and the solvents used in wide range.展开更多
Towards the development of potential new organic photovoltaic and optoelectronic materials, a simple route to synthesize flexibly ether linked fullerene-bis[oligo-(phenylene-alt-thiophene)] and evaluation of electroch...Towards the development of potential new organic photovoltaic and optoelectronic materials, a simple route to synthesize flexibly ether linked fullerene-bis[oligo-(phenylene-alt-thiophene)] and evaluation of electrochemical, photophysical and magnetic properties is presented. Flexible ether linking of oligo-phenylene-thiophene chain to 1, 2 C60(OH)2 is achieved employing Williamson’s ether synthesis. 7-chain phenylene-thiophene chain fluorescent conducting oligomer is synthesized using Grignard coupling reaction with preservation of bromo end groups. Oligomer is highly ordered and soluble in all organic solvents while on linking to fullerene-diol, solubility of adduct restricts only to dimethyl sulfoxide (DMSO). All the synthesized materials are characterized through spectroscopic techniques and molecular weight is determined by mass spectrometry and GPC. Properties of the material indicate the substantial effect of fullerene. High quenching in fluorescence intensity and strong paramagnetic property are observed in this material.展开更多
Alternating copolymerization of 9,9-dihexyl-2,7-dibromofluorene, N-hexyl-2,7-dibromocarbazole (HCz) with diethynyldimethylsilane, diethynyldiphenylsilane, has been investigated using Sonogashira coupling reaction. Pho...Alternating copolymerization of 9,9-dihexyl-2,7-dibromofluorene, N-hexyl-2,7-dibromocarbazole (HCz) with diethynyldimethylsilane, diethynyldiphenylsilane, has been investigated using Sonogashira coupling reaction. Photophysical properties of the resulting copolymers were investigated with UV-Vis absorption and photoluminescence spectroscopy. All the copolymers in chloro-form solution showed absorption peaks at 270 - 280 nm with shoulder peaks at around 380 nm derived from π-π* transition or intra-molecular charge transfer through σ-π moiety, respectively. The chloroform solutions of the copolymers showed broad emission peaks at 415 - 425 nm. The emission wave lengths of the copolymers in the solid state (cast film) detected at 360 - 385 nm were remarkably blue-shifted in comparison with those in the chloroform solutions. Hydrosilylation reaction of the copolymers with 1,4-bis(dimethylsilyl)benzene yielded networked copolymers soluble in chloroform, indicating formation of branching polymers. The chloroform solutions of the HCz-based networked copolymers showed bimodal emission derived from new highly energy states in the σ-π conjugation.展开更多
The perylene diimide derivatives（s-THBPDI and d-THBPDI） bearing oxygen bridged twisty heptatomic biphenyl in the bay positions of the perylene core through acetylene bond were designed and synthesized.The photophysi...The perylene diimide derivatives（s-THBPDI and d-THBPDI） bearing oxygen bridged twisty heptatomic biphenyl in the bay positions of the perylene core through acetylene bond were designed and synthesized.The photophysical properties of the functionalized dyes were investigated in solution and solid state by UV-vis and photoluminescence（PL） spectra.Their UV-vis and PL spectrum both exhibited the different concentration-dependent behaviors due to the difference of chemical structure.Moreover,cyclic voltammetry results indicated that the introduction of oxygen bridged twisted heptatomic biphenyl could decrease the LUMO energy level of the perylene diimide effectively and made it promising material in photoelectric devices.展开更多
A series of poly（aryleneethynylene）s containing dibenzosilole unit has been synthesized by palladium-catalyzed Sonogashira cross-coupling reactions with 2,7-diethynyl-9,9-dihexyl-3,6-dimethoxy-9H-dibenzosilole （4）...A series of poly（aryleneethynylene）s containing dibenzosilole unit has been synthesized by palladium-catalyzed Sonogashira cross-coupling reactions with 2,7-diethynyl-9,9-dihexyl-3,6-dimethoxy-9H-dibenzosilole （4） as the key monomer. Their photophysical properties in solution were investigated. All of the polymers showed intense fluorescence with high quantum efficiencies.展开更多
基金supported by the National Natural Science Foundation of China(Nos.21776207 and 21576195)。
文摘Molecular engineering is a crucial strategy for improving the photovoltaic performance of dye-sensitized solar cells(DSSCs). Despite the common use of the donor-π bridge-acceptor architecture in designing sensitizers, the underlying structure-performance relationship remains not fully understood. In this study, we synthesized and characterized three sensitizers: MOTP-Pyc, MOS_(2)P-Pyc, and MOTS_(2)P-Pyc, all featuring a bipyrimidine acceptor. Absorption spectra, cyclic voltammetry, and transient photoluminescence spectra reveal a photo-induced electron transfer(PET) process in the excited sensitizers. Electron spin resonance spectroscopy confirmed the presence of charge-separated states. The varying donor and π-bridge structures among the three sensitizers led to differences in their conjugation effect, influencing light absorption abilities and PET processes and ultimately impacting the photovoltaic performance. Among the synthesized sensitizers, MOTP-Pyc demonstrated a DSSC efficiency of 3.04%. Introducing an additional thienothiophene block into the π-bridge improved the DSSC efficiency to 4.47% for MOTS_(2)P-Pyc. Conversely, replacing the phenyl group with a thienothiophene block reduced DSSC efficiency to 2.14% for MOS_(2)P-Pyc. Given the proton-accepting ability of the bipyrimidine module, we treated the dye-sensitized TiO_(2) photoanodes with hydroiodic acid(HI), significantly broadening the light absorption range. This treatment greatly enhanced the short-circuit current density of DSSCs owing to the enhanced electron-withdrawing ability of the acceptor. Consequently, the HI-treated MOTS_(2)P-Pyc-based DSSCs achieved the highest power conversion efficiency of 7.12%, comparable to that of the N719 dye at 7.09%. This work reveals the positive role of bipyrimidine in the design of organic sensitizers for DSSC applications.
基金financially supported by the National Natural Science Foundation of China(Nos.22271116 and 22071079 for M.W)Jilin Provincial Science and Technology Department(No.20230101027JC for M.W.)the fellowship of China Postdoctoral Science Foundation(No.2021M701383 for J.S)。
文摘The stable coordinated metallo-complexes based on 2,2′:6′,2″-terpyridine(tpy)and its derivatives have been widely researched for various wide-ranging applications in photoelectronics,catalysis,sensor,photoluminescence,and so on.However,the most reported studies ignored the comprehensive comparison between structures modified by different positions and photoluminescence.Herein,we design a series of metallo-complexes which were assembled with tpy substituted triphenylamine(TPA)at different positions and metal ions and explored their photophysical properties.In the solution state,MLE_(2)based on the 5,5″-positions modification showed the highest PLQYs and PL intensity.With the increase of solvent polarity,MLB2exhibit the largest redshift.In the solid state,from MLA_(2)to MLE_(2),the emission colours are gradually red-shifted from yellow to red.The findings in this work may pave a new way to design functional metallo-complexes,not just for PL properties.
基金supported by the NSFC(82172081 and 52103168)the Science and Technology Program of Tianjin,China(21JCZDJC00970 and 22JCQNJC01640)Tianjin Key Medical Discipline(Specialty)Construction Project,and the Fundamental Research Funds for the Central Universities(63243137).
文摘Precision medicine calls for advanced theranostics that integrate controllable diagnostic and therapeutic capabilities into one platform for disease treatment in the early stage.Phototheranostics such as fluorescence imaging(FLI),photoacoustic imaging(PAI),photodynamic therapy(PDT),and photothermal therapy(PTT)have attracted considerable attention in recent years,which mainly employ different excited-state energy dissipation pathways of a chromophore.According to the Jablonski diagram,FLI is related to the radiative process,PAI and PTT are derived from the nonradiative thermal deactivation,and PDT originates from the triplet state energy,in which these processes are usually competitive.Therefore,it is critically important to precisely tune the photophysical energy transformation processes to realize certain diagnosis and treatment properties in optimal state for boosting biomedical applications.Currently,there are mainly two strategies including chemical structure and aggregate behavior changes that relate to the regulation of excited state energy dissipation.In this review,we will discuss the recent advances of smart molecular probes that the photophysical properties can be regulated by external triggers and their applications in biomedical fields.We will summarize the development of activatable phototheranostic molecular probes in response to stimuli such as reactive oxygen species,pH,light,hypoxia,enzyme and gas.The assembly and disassembly of molecular aggregates that greatly affect the photophysical energy transformation processes will also be highlighted.This review aims to provide valuable insights into the development of more accurate diagnostic and therapeutic systems,thereby advancing the emerging field of smart medicine.
文摘Synthesis, IR spectra, UV vis spectra and photophysical properties of Gd 3+ , Eu 3+ , Tb 3+ complexes with 3,4 furandicarboxylic acid and 1,10 phenanthroline are reported. Intramolecular energy transfer process for these complexes is discussed in detail. It is found that the intramolecular energy transfer efficiency depends on the relative positions between the resonance energy levels of the central rare earth ions and the lowest triplet state energies of ligands.
基金Project supported by the Hunan Province Education Research Foundation of China (04C640)
文摘The polymeric ligand PBIa （functionalized polybenzimidazole containing β-diketone side group） was successfully synthesized via the reaction of polybenzimidazole （PBI） with 3-Br-acetylacetone in DM SO solvent using Nail as the deprotonation reagent. Its corresponding polymeric complexes of Dy^3＋ and Gd^3＋ were prepared and characterized by FT-IR, ^1H NMR, molar conductance measurements, and thermal analysis. The photoluminescence properties and the probable mechanism of the Dy and Gd complexes were studied. The measurement and analysis of the thermal properties showed that these were thermal stable.
基金This study was supported by the National Natural Science Foundation of China （No. 20604007）；Natural Science Foundation of Fujian （No. C0510007）；Key Foundation for Ministry of Education （No. 206071）；Key Foundation for Education 0ffice of Fujian （No. JA05195）；Key Laboratory for Structure Chemistry （No. 040083）.
文摘A novel anthraquinone phthalocyanine AI（Ⅲ） 4 and Co（Ⅱ） 5 were synthesized and characterized by elemental analysis, IR UV/ vis, ^1H NMlL HPLC and MS. The photophysical properties of the two metal complexes were studied and compared by fluorescence spectrum method.
基金supported by the National Natural Science Foundation of China(Nos.61631166001,11574181,11774204)Key R&D Programs of Shandong Province,China(No.2018GGX103004)support from the ARC Centre of Excellence in Exciton Science(No.CE170100026)
文摘The composition ratio of donor and acceptor materials in organic bulk heterojunction (BHJ) is one of the key parameters to govern the performance in organic solar cells (OSCs). Therefore, high-performance non-fullerene organic bulk heterojunction consisting of poly[(2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b' ]dithiophene))-co-(1,3-di(5-thiophene-2-yl)–5,7-bis(2-ethylhexyl) benzo[1,2-c:4,5-c']dithiophene-4,8-dione)] (PBDB-T) and 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))–5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2' ,3'-d' ]-s-indaceno[1,2-b:5,6-b' ]-dithio-phene (ITIC) are used to investigate the correlation among various donor: acceptor (D:A) ratios, photophysical properties and photovoltaic performance. Interestingly, the function of short-circuit current (Jsc) and D:A ratios demonstrates an axisymmetric trend. When the blending ratio of D:A deviates from the optimal ratio, the symmetrically decreased Jsc is derived from a reduction in the D:A interface or amorphous region. Research on the steady-state photoluminescence (PL), the time-resolved fluorescence spectroscopy measurements, atomic force microscopic (AFM) and grazing-incidence small angle X-rays scattering (GIWAXS) indicates no significant variation in energy loss in the process of changing D:A ratios in BHJs. With high donor or acceptor content, the domain size improves significantly, but the distance of π-π stacking corresponding to molecular packing has not changed significantly, and the bi-continuous percolation pathways were not obviously influenced.
文摘One ternary complex of europium with the plant growth regulator HDPHA (2-Hydroxydiphenyl acetic acid) and Phen (1,10-Phenanthroline), Eu(DPHA) 3·Phen·2H 2O, was synthesized and characterized by the elemental analysis and DTA-TG measurement. The photophysical property of the complex was investigated by means of IR spectra, Raman spectrum and laser-exited, high-resolved excitation and emission spectra as well as time-resolved luminescence spectra. The luminescence spectra reveal four Eu 3+ sites with energy difference within 25 cm -1 and local symmetries of C 1 or C 2 or C s in the complex. The energy transfer among the Eu 3+ sites is observed. The 7F J sublevel splitting of the Eu 3+ ion is discussed.
基金supported financially by National Natural Science Foundation of China(Nos.20774039,20872061)the National Basic Research(No.2007CB925103)
文摘A novel octupolar chromophore with 1,3,5-triazine as core,2,7-divinylene-9,9-dimethylfluorene as extendedπ-conjugated bridge,triarylamine as the electron-donating end-groups was successfully synthesized and characterized.Their linear photophysical and two-photon absorption（TPA） properties were investigated by UV absorption,excited fluorescence（SPEF） spectra and nonlinear transmission method,respectively.The absorption cut-off of the chromophore is below 520 nm and it has stronger fluorescence emission in a nonpolar solvent.In addition,the chromophore exhibits larger TPA cross-section（226.0 GM） in the femtosecond regime at 800 nm.
基金Beijing Natural Science Foundation(No.2093033)Scientific Research Project of Beijing Educational Committee(No.KM200910020012) for financial support.
文摘A series of linear and V-shaped oligo(phenylene ethynylene) derivatives 1-3 were synthesized through sequent Sonogashira coupling and propargyl alcohol deprotection reaction in high yields.The alkoxy chains(i.e.,n-hexyloxy groups) were introduced to assure good solubility of compounds 1-3 in common solvents.The photophysical properties of 1-3 in solution depend strongly on the geometries of these compounds.
基金supported by the National Natural Science Foundation of China(No.21773238)the Fundamental Research Funds of Shandong University(2019GN025)。
文摘Excited-state intramolecular proton transfer(ESIPT)is favored by researchers because of its unique optical properties.However,there are relatively few systematic studies on the effects of changing the electronegativity of atoms on the ESIPT process and photophysical properties.Therefore,we selected a series of benzoxazole isothiocyanate fluorescent dyes(2-HOB,2-HSB,and 2-HSe B)by theoretical methods,and systematically studied the ESIPT process and photophysical properties by changing the electronegativity of chalcogen atoms.The calculated bond angle,bond length,energy gap,and infrared spectrum analysis show that the order of the strength of intramolecular hydrogen bonding of the three molecules is 2-HOB<2-HSB<2-HSe B.Correspondingly,the magnitude of the energy barrier of the potential energy curve is 2-HOB>2-HSB>2-HSe B.In addition,the calculated electronic spectrum shows that as the atomic electronegativity decreases,the emission spectrum has a redshift.Therefore,this work will offer certain theoretical guidance for the synthesis and application of new dyes based on ESIPT properties.
基金financially supported by the National Natural Science Foundation of China(Nos.21671068,81400023,61178037,81273549)National Basic Research Program(973 Program)of China(No.2013CB922403)the Open Fund of State Key Laboratory of Optoelectronic Materials and Technologies,Sun Yatsen University(No.OEMT-2015-KF-05)
文摘A new 2-chloro-5,10,15-tris（2,4,6-triphenylphenyl）-corrole was accidentally synthesized in an acceptable yield of 5.7% during the synthesis of its parent corrole, in which DDQ served as oxidant and chlorinating agent. The compound was well characterized by X-ray diffraction analysis,;H NMR, mass spectroscopy and absorption spectroscopy. Photophysical properties tests revealed that the chlorination caused a sharp decrease in fluorescence intensity, fluorescence life time, and fluorescence quantum yield.Electrochemical investigation demonstrated the positive shift of redox potentials for chlorinated corrole as compared to non-chlorinated corrole.
基金the National Natural Science Foundation of China(No.21174042)Fund of Project on the Integration of Industry,Education and Research of Guangdong Province(No.2013B090500072)
文摘A diquinoxalinopyrene （DQP） derivative and the corresponding oligomers （PDQPs） with Mn of ca. 3300, 4200, 5600, and 7300 have been synthesized. It is found that the band gaps and highest occupied molecular orbital （HOMO）/lowest unoccupied molecular orbital （LUMO） levels between DQP and its homopolymers only have a slight difference, implying a limited conjugation extension achieved from unimer to heptamer. The DFT calculation is in accordance with the experimental results. It reveals that the nodal planes are across the 2,11-positions in the LUMO and/or HOMO of DQP, dimer and trimer, which can be used to explain this special phenomenon.
文摘The porphyrin-like macrocycles and their metal complexes are s novel family of photoresponsive molecules.The properties of the excited states,both singlet and triplet are investigated by the stationary and transient processes.
文摘A new type of anthracene crown ether 1, 8-anthraceno-18-crown-5 has been synthesizedand the photophysical properties upon complexation with alkali and alkaline-earth metal canonswere investigated. The fiuorescence quantum yield and lifetime are appreciably enhanced, and thestability constant Ks were determined by fluorometric titration. It was found that the magnitude ofKs is controlled by the size and charge density of the complexed canons.
基金This work is supported by the National Natural Science Foundation of China and Tulane University
文摘The photophysical behaviors of the oligomer based on 1,1'-binaphthol with3,3'-acetylene spacer were investigated. The oligomer molecule has a naphthyl-acetylene-naphthyl effective conjugation segment. The atropic of the 1,1'-binaphthyl moiety led totwisted and rigid main chain in the oligomer. With the changes of the external environ-ment such as solvents used, solvent viscosity and ambient temperature, the wavelengthsof absorption and the intensities of fluorescence and absorption are changed slightly, butthe fluorescent intensity and quantum yield can be influenced. The luminescent behav-iors of the oligomer exhibit twisted intramolecular charge transfer characteristics, whichcould have a potential application in wavelength-stable light emitting material adaptableto ambient temperature and the solvents used in wide range.
文摘Towards the development of potential new organic photovoltaic and optoelectronic materials, a simple route to synthesize flexibly ether linked fullerene-bis[oligo-(phenylene-alt-thiophene)] and evaluation of electrochemical, photophysical and magnetic properties is presented. Flexible ether linking of oligo-phenylene-thiophene chain to 1, 2 C60(OH)2 is achieved employing Williamson’s ether synthesis. 7-chain phenylene-thiophene chain fluorescent conducting oligomer is synthesized using Grignard coupling reaction with preservation of bromo end groups. Oligomer is highly ordered and soluble in all organic solvents while on linking to fullerene-diol, solubility of adduct restricts only to dimethyl sulfoxide (DMSO). All the synthesized materials are characterized through spectroscopic techniques and molecular weight is determined by mass spectrometry and GPC. Properties of the material indicate the substantial effect of fullerene. High quenching in fluorescence intensity and strong paramagnetic property are observed in this material.
文摘Alternating copolymerization of 9,9-dihexyl-2,7-dibromofluorene, N-hexyl-2,7-dibromocarbazole (HCz) with diethynyldimethylsilane, diethynyldiphenylsilane, has been investigated using Sonogashira coupling reaction. Photophysical properties of the resulting copolymers were investigated with UV-Vis absorption and photoluminescence spectroscopy. All the copolymers in chloro-form solution showed absorption peaks at 270 - 280 nm with shoulder peaks at around 380 nm derived from π-π* transition or intra-molecular charge transfer through σ-π moiety, respectively. The chloroform solutions of the copolymers showed broad emission peaks at 415 - 425 nm. The emission wave lengths of the copolymers in the solid state (cast film) detected at 360 - 385 nm were remarkably blue-shifted in comparison with those in the chloroform solutions. Hydrosilylation reaction of the copolymers with 1,4-bis(dimethylsilyl)benzene yielded networked copolymers soluble in chloroform, indicating formation of branching polymers. The chloroform solutions of the HCz-based networked copolymers showed bimodal emission derived from new highly energy states in the σ-π conjugation.
基金supported by the National Natural Science Foundation of China (Nos: 51173155,51472214)the Colleges and Universities Science and Technology Research Project of Hebei Province (No.QN20131070)
文摘The perylene diimide derivatives（s-THBPDI and d-THBPDI） bearing oxygen bridged twisty heptatomic biphenyl in the bay positions of the perylene core through acetylene bond were designed and synthesized.The photophysical properties of the functionalized dyes were investigated in solution and solid state by UV-vis and photoluminescence（PL） spectra.Their UV-vis and PL spectrum both exhibited the different concentration-dependent behaviors due to the difference of chemical structure.Moreover,cyclic voltammetry results indicated that the introduction of oxygen bridged twisted heptatomic biphenyl could decrease the LUMO energy level of the perylene diimide effectively and made it promising material in photoelectric devices.
基金the National Natural Science Foundation of China(NSFC,Nos.50673094 and 20774102) for financial support
文摘A series of poly（aryleneethynylene）s containing dibenzosilole unit has been synthesized by palladium-catalyzed Sonogashira cross-coupling reactions with 2,7-diethynyl-9,9-dihexyl-3,6-dimethoxy-9H-dibenzosilole （4） as the key monomer. Their photophysical properties in solution were investigated. All of the polymers showed intense fluorescence with high quantum efficiencies.
