4,4-Difluoro-4-bora-3a,4a-diaza-sindacene (BODIPY) is a sort of photofunctional dye which possesses advantages including strong light-capturing property, high photon-resistance, etc. Meso-N substituted aza-BODIPY is a...4,4-Difluoro-4-bora-3a,4a-diaza-sindacene (BODIPY) is a sort of photofunctional dye which possesses advantages including strong light-capturing property, high photon-resistance, etc. Meso-N substituted aza-BODIPY is a crucial derivative of BODIPY scaffold that has the favorable optical properties and a significant spectral redshift. The photophysical properties can be tuned by molecular design, and the attenuation path of the excited state energy release of absorbed light energy can be well controlled via structural modifications, enabling tailored application. It has been extensively employed in life medicine fields including fluorescence imaging diagnosis, photodynamic therapy photosensitizer and photothermal therapy reagent and so forth. Extensive research and review have been performed in these areas. However, BODIPYs/aza-BODIPYs have a significant role in energy, catalysis, optoelectronics, photo-responsive materials and other fields. Nevertheless, there are relatively few studies and reviews in these fields on the modification and application based on BODIPY/aza-BODIPY scaffold. Herein, in this review we summarized the application of BODIPY/aza-BODIPY in the aforementioned fields, with the molecular regulation of dye as the foundation and the utilization in the above fields as the objective, in the intention of providing inspiration for the exploration of innovative BODIPY/aza-BODIPY research in the field of light resource conversion and functional materials.展开更多
Fluorescent dyes play a crucial role in fluorescence imaging and sensing technology.However,there is a dilemma that they are usually intrinsically hydrophobic which lacks of emission in water and modification with ion...Fluorescent dyes play a crucial role in fluorescence imaging and sensing technology.However,there is a dilemma that they are usually intrinsically hydrophobic which lacks of emission in water and modification with ionic groups to access water solubility may result in poor membrane permeability.Fluorescent dyes with strong fluorescence emission in both nonpolar and polar solvents are highly desirable.In this manuscript,we reported a strategy to develop fluorescent BODIPY dyes via installation of amide moiety at meso position of 1,3,5,7-tetramethyl-BODIPY and discovered that N,N'-dialkylsubstituted BODIPY amides possessed highly fluorescent emission with favorable environment-insensitive properties.展开更多
Sugar-O-BODIPY conjugates,in which the fluorescent dye O-BODIPY is linked to sugars directly through B-O-C bonds,have been synthesized via an acid-catalyzed transesterification procedure.Conjugates of glucose,xylose a...Sugar-O-BODIPY conjugates,in which the fluorescent dye O-BODIPY is linked to sugars directly through B-O-C bonds,have been synthesized via an acid-catalyzed transesterification procedure.Conjugates of glucose,xylose and ribose with O-BODIPYs bearing meso-p-tolyl and meso-mesityl substituents were prepared.展开更多
Helicene-type compounds are renowned for their unique chiral properties,however,obtaining their enantiomers usually requires laborious and costly chiral separations.Moreover,their chiroptical activity is typically lim...Helicene-type compounds are renowned for their unique chiral properties,however,obtaining their enantiomers usually requires laborious and costly chiral separations.Moreover,their chiroptical activity is typically limited to the ultraviolet spectral range,which restricts their broader applicability.To overcome these limitations,a novel and efficient strategy for synthesizing optically active compounds through the incorporation of an optically pure binaphthol(BINOL)group onto the periphery of β-isoindigo based aza dipyrrometheneboron difluoride(aza-BODIPY)analogues(BIABs)was presented.The resulting(R)/(S)-BINOL-BIABs demonstrate exceptional photostability,deep-red emission,strong Cotton effect(Δε)and high absorbance dissymmetry factor(g_(abs)).Moreover,tunable circularly polarized luminescence(CPL)with high brightness in the deep-red region was achieved.This strategy offers straightforward procedures for synthesizing optically active compounds.展开更多
The development of cost-effective,environmentally sustainable narrowband near-infrared(NIR)organic light-emitting diodes(OLEDs)remains challenging due to low intrinsic quantum yields of NIR emitters,as constrained by ...The development of cost-effective,environmentally sustainable narrowband near-infrared(NIR)organic light-emitting diodes(OLEDs)remains challenging due to low intrinsic quantum yields of NIR emitters,as constrained by the energy gap law and inefficient triplet exciton utilization.In this study,we present a conformation-locking strategy combined with donor engineering to enhance NIR emitters based on a boron-dipyrromethene(BODIPY)scaffold for high-performance solution-processed OLEDs.Two NIR emitters,Ph-BDP-Cz and Ph-BDP-PY,were synthesized by introducing a donor at the α-position of the BODIPY core via a vinyl bridge.This design increases molecular rigidity by promoting HF interactions between vinyl hydrogens and the BF2 group,suppressing twisting and scissoring motions,which results in narrow emission and high photoluminescence quantum yields.Donor engineering also enables fine-tuning of emission wavelengths without broadening the full-width at half-maximum(FWHM),maintaining a narrow emission profile.Using these BODIPY emitters in thermally activated delayed fluorescence(TADF)-sensitized hyperfluorescent OLEDs,we achieved a maximum external quantum efficiency(EQE)of 6.9%with an emission peak at 702 nm and a narrow FWHM of<45 nm.To our knowledge,this represents one of the highest efficiencies among TADF sensitized solution-processed NIR OLEDs,offering a promising path toward the development of sustainable and high-performance NIR optoelectronic devices.展开更多
The development of highly effective photosensitizers(PSs)based on supramolecular coordination complexes(SCCs)is highly appealing in supramolecular chemistry,materials science,and biology.SCCs offer promising platforms...The development of highly effective photosensitizers(PSs)based on supramolecular coordination complexes(SCCs)is highly appealing in supramolecular chemistry,materials science,and biology.SCCs offer promising platforms for incorporating multiple PSs and other functional units into their well-defined structures,allowing for precise control over the number and distribution of these components.In this study,we present an efficient and straightforward method for modulating the photosensitization process of PSs derived from a family of BF_(2)-chelated dipyrromethene(BODIPY)-containing Pt(Ⅱ)metallacycles by varying pre-designed Pt(Ⅱ)acceptors.By utilizing different Pt(Ⅱ)acceptors with varying Pt atom configurations and degrees ofπ-conjugated organic moieties,we observed tunable characteristics in the photosensitization process and singlet oxygen(^(1)O_(2))generation efficiency of these targeted metallacycles.Furthermore,we successfully conducted the visible-light-driven oxidative coupling of various amines to imines,catalyzed by the prepared metallacycle PSs.This study offers a novel approach for fabricating efficient PSs based on SCCs,featuring tunable photosensitization efficiency and excellent photocatalytic reactivity,while providing new insights into the preparation of effective PSs.展开更多
Bacterial infections pose a significant threat to human health and entail substantial economic losses.Due to the broad-spectrum antibacterial effect and low susceptibility to drug resistance,photodynamic therapy(PDT),...Bacterial infections pose a significant threat to human health and entail substantial economic losses.Due to the broad-spectrum antibacterial effect and low susceptibility to drug resistance,photodynamic therapy(PDT),a nontraditional antibacterial approach,has garnered a lot of attention.In PDT,the selection of photosensitizer(PS)is crucial because it directly affects the efficiency and safety of the treatment.As a versatile fluorophore,the advantages of 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene(BODIPY)used as a PS for antibacterial PDT are mainly reflected in its high quantum yield of singlet oxygen,easy modification,and exceptional photostability.Through strategic chemical modifications of the BODIPY structures,it is possible to enhance their photodynamic antibacterial activity and refine their selectivity for bacterial killing.This review focuses on the application of BODIPY-based PSs for treating bacterial infections.According to the design strategies of photodynamic antibacterial materials incorporating BODIPY,a variety of representative therapeutic agents having emerged in recent years are classified and discussed,aiming to offer insights for future research and development in this field.展开更多
We compared a range of BODIPY dimer derivatives without installing blocking groups by optimizing geometry structures and analyzing energies,frontier mo-lecular orbitals,Chole&Cele map,electron density difference,s...We compared a range of BODIPY dimer derivatives without installing blocking groups by optimizing geometry structures and analyzing energies,frontier mo-lecular orbitals,Chole&Cele map,electron density difference,spin-orbit coupling(SOC)matrix and decay rate constants from excited states.The dihedral angles of theβ-β-linked BODIPY dimer and theα-α-linked BODIPY dimer tend to flatten in the T_(1)state,which is detrimental to the occurrence of the intersystem crossing(ISC).Conversely,the dihedral angle of the meso-β-linked BODIPY dimer,the meso-meso-linked BODIPY dimer andα-γ-linked BODIPY dimer is within the range of 125°-143°in the T_(1)state,facilitating ISC and the generation of singlet oxygen.Notably,the transition from S1 to S0 involving lowest unoccupied mo-lecular orbital to highest occupied molecular orbital with long-wavelength emis-sion and moderate oscillator strength underpins the remarkable long emission peaks observed experimentally forα-γ-linked BODIPY dimer.Moreover,the apparent SOC matrix enhances the ISC process,resulting in a respectable effi-ciency in generating singlet oxygen for this dimer.In meso-β-linked BODIPY,meso-meso-linked BODIPY,andα-γ-linked BODIPY,the S_(1)→T_(1)process is characterized by a significant charge transfer,specifically transitioning from the^(1)CT state to the^(3)LE state,indicative of a spin-orbit charge transfer ISC(SOCTISC)mechanism.The ability to regulate the photosensitivity of BODIPY dimers by adjusting the dihedral angle between the two units in the T_(1)state unveils new avenues for designing high-performance photosensitizers for both therapeutic and imaging applications.展开更多
Highly toxic phosgene,diethyl chlorophosphate(DCP)and volatile acyl chlorides endanger our life and public security.To achieve facile sensing and discrimination of multiple target analytes,herein,we presented a single...Highly toxic phosgene,diethyl chlorophosphate(DCP)and volatile acyl chlorides endanger our life and public security.To achieve facile sensing and discrimination of multiple target analytes,herein,we presented a single fluorescent probe(BDP-CHD)for high-throughput screening of phosgene,DCP and volatile acyl chlorides.The probe underwent a covalent cascade reaction with phosgene to form boron dipyrromethene(BODIPY)with bright green fluorescence.By contrast,DCP,diphosgene and acyl chlorides can covalently assembled with the probe,giving rise to strong blue fluorescence.The probe has demonstrated high-throughput detection capability,high sensitivity,fast response(within 3 s)and parts per trillion(ppt)level detection limit.Furthermore,a portable platform based on BDP-CHD was constructed,which has achieved high-throughput discrimination of 16 analytes through linear discriminant analysis(LDA).Moreover,a smartphone adaptable RGB recognition pattern was established for the quantitative detection of multi-analytes.Therefore,this portable fluorescence sensing platform can serve as a versatile tool for rapid and high-throughput detection of toxic phosgene,DCP and volatile acyl chlorides.The proposed“one for more”strategy simplifies multi-target discrimination procedures and holds great promise for various sensing applications.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22078201,U1908202)Liaoning&Shenyang Key Laboratory of Functional Dye and Pigment(Nos.2021JH13/10200018,21-104-0-23)。
文摘4,4-Difluoro-4-bora-3a,4a-diaza-sindacene (BODIPY) is a sort of photofunctional dye which possesses advantages including strong light-capturing property, high photon-resistance, etc. Meso-N substituted aza-BODIPY is a crucial derivative of BODIPY scaffold that has the favorable optical properties and a significant spectral redshift. The photophysical properties can be tuned by molecular design, and the attenuation path of the excited state energy release of absorbed light energy can be well controlled via structural modifications, enabling tailored application. It has been extensively employed in life medicine fields including fluorescence imaging diagnosis, photodynamic therapy photosensitizer and photothermal therapy reagent and so forth. Extensive research and review have been performed in these areas. However, BODIPYs/aza-BODIPYs have a significant role in energy, catalysis, optoelectronics, photo-responsive materials and other fields. Nevertheless, there are relatively few studies and reviews in these fields on the modification and application based on BODIPY/aza-BODIPY scaffold. Herein, in this review we summarized the application of BODIPY/aza-BODIPY in the aforementioned fields, with the molecular regulation of dye as the foundation and the utilization in the above fields as the objective, in the intention of providing inspiration for the exploration of innovative BODIPY/aza-BODIPY research in the field of light resource conversion and functional materials.
基金supported by the National Natural Science Foundation of China(No.82030107)。
文摘Fluorescent dyes play a crucial role in fluorescence imaging and sensing technology.However,there is a dilemma that they are usually intrinsically hydrophobic which lacks of emission in water and modification with ionic groups to access water solubility may result in poor membrane permeability.Fluorescent dyes with strong fluorescence emission in both nonpolar and polar solvents are highly desirable.In this manuscript,we reported a strategy to develop fluorescent BODIPY dyes via installation of amide moiety at meso position of 1,3,5,7-tetramethyl-BODIPY and discovered that N,N'-dialkylsubstituted BODIPY amides possessed highly fluorescent emission with favorable environment-insensitive properties.
基金This work was supported by Marsden Fund grant UOA1521,administered by the Royal Society Te Apārangi.DK and MJW thank the Marsden Fund and MHG thanks the University of Auckland for the award of doctoral scholarships.The authors thank Dr Paul Hume and Associate Professors Mattie S.M.Timmer and Bridget L.Stocker(Victoria University of Wellington)for assistance with photophysical measurements and advice on NMR techniques.
文摘Sugar-O-BODIPY conjugates,in which the fluorescent dye O-BODIPY is linked to sugars directly through B-O-C bonds,have been synthesized via an acid-catalyzed transesterification procedure.Conjugates of glucose,xylose and ribose with O-BODIPYs bearing meso-p-tolyl and meso-mesityl substituents were prepared.
文摘Helicene-type compounds are renowned for their unique chiral properties,however,obtaining their enantiomers usually requires laborious and costly chiral separations.Moreover,their chiroptical activity is typically limited to the ultraviolet spectral range,which restricts their broader applicability.To overcome these limitations,a novel and efficient strategy for synthesizing optically active compounds through the incorporation of an optically pure binaphthol(BINOL)group onto the periphery of β-isoindigo based aza dipyrrometheneboron difluoride(aza-BODIPY)analogues(BIABs)was presented.The resulting(R)/(S)-BINOL-BIABs demonstrate exceptional photostability,deep-red emission,strong Cotton effect(Δε)and high absorbance dissymmetry factor(g_(abs)).Moreover,tunable circularly polarized luminescence(CPL)with high brightness in the deep-red region was achieved.This strategy offers straightforward procedures for synthesizing optically active compounds.
基金financially supported by Natural Science Foundation of Guangdong Province(No.2022B1515020041)National Natural Science Foundation of China(Nos.22350410384,52273179,52303228,U23A20594)+1 种基金Guangzhou Basic and Applied Basic Research(No.2023A04J1374)the Instrumental Analysis Center of Guangdong University of Technology for their support。
文摘The development of cost-effective,environmentally sustainable narrowband near-infrared(NIR)organic light-emitting diodes(OLEDs)remains challenging due to low intrinsic quantum yields of NIR emitters,as constrained by the energy gap law and inefficient triplet exciton utilization.In this study,we present a conformation-locking strategy combined with donor engineering to enhance NIR emitters based on a boron-dipyrromethene(BODIPY)scaffold for high-performance solution-processed OLEDs.Two NIR emitters,Ph-BDP-Cz and Ph-BDP-PY,were synthesized by introducing a donor at the α-position of the BODIPY core via a vinyl bridge.This design increases molecular rigidity by promoting HF interactions between vinyl hydrogens and the BF2 group,suppressing twisting and scissoring motions,which results in narrow emission and high photoluminescence quantum yields.Donor engineering also enables fine-tuning of emission wavelengths without broadening the full-width at half-maximum(FWHM),maintaining a narrow emission profile.Using these BODIPY emitters in thermally activated delayed fluorescence(TADF)-sensitized hyperfluorescent OLEDs,we achieved a maximum external quantum efficiency(EQE)of 6.9%with an emission peak at 702 nm and a narrow FWHM of<45 nm.To our knowledge,this represents one of the highest efficiencies among TADF sensitized solution-processed NIR OLEDs,offering a promising path toward the development of sustainable and high-performance NIR optoelectronic devices.
基金the financial support by the National Natural Science Foundation of China(Nos.22301081,22301269 and 22401096)China Postdoctoral Science Foundation(No.2023M731095)+4 种基金the Shanghai Frontiers Science Center for Molecular Intelligent Synthesesthe Fundamental Research Funds for the Central UniversitiesYoung Talent Fund of Association for Science and Technology in Shaanxi,China(No.20240628)Scientific Research Program Funded by Education Department of Shaanxi Provincial Government(No.23JK0752)Foundation of Yulin Association for Science and Technology(No.20230512)。
文摘The development of highly effective photosensitizers(PSs)based on supramolecular coordination complexes(SCCs)is highly appealing in supramolecular chemistry,materials science,and biology.SCCs offer promising platforms for incorporating multiple PSs and other functional units into their well-defined structures,allowing for precise control over the number and distribution of these components.In this study,we present an efficient and straightforward method for modulating the photosensitization process of PSs derived from a family of BF_(2)-chelated dipyrromethene(BODIPY)-containing Pt(Ⅱ)metallacycles by varying pre-designed Pt(Ⅱ)acceptors.By utilizing different Pt(Ⅱ)acceptors with varying Pt atom configurations and degrees ofπ-conjugated organic moieties,we observed tunable characteristics in the photosensitization process and singlet oxygen(^(1)O_(2))generation efficiency of these targeted metallacycles.Furthermore,we successfully conducted the visible-light-driven oxidative coupling of various amines to imines,catalyzed by the prepared metallacycle PSs.This study offers a novel approach for fabricating efficient PSs based on SCCs,featuring tunable photosensitization efficiency and excellent photocatalytic reactivity,while providing new insights into the preparation of effective PSs.
文摘Bacterial infections pose a significant threat to human health and entail substantial economic losses.Due to the broad-spectrum antibacterial effect and low susceptibility to drug resistance,photodynamic therapy(PDT),a nontraditional antibacterial approach,has garnered a lot of attention.In PDT,the selection of photosensitizer(PS)is crucial because it directly affects the efficiency and safety of the treatment.As a versatile fluorophore,the advantages of 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene(BODIPY)used as a PS for antibacterial PDT are mainly reflected in its high quantum yield of singlet oxygen,easy modification,and exceptional photostability.Through strategic chemical modifications of the BODIPY structures,it is possible to enhance their photodynamic antibacterial activity and refine their selectivity for bacterial killing.This review focuses on the application of BODIPY-based PSs for treating bacterial infections.According to the design strategies of photodynamic antibacterial materials incorporating BODIPY,a variety of representative therapeutic agents having emerged in recent years are classified and discussed,aiming to offer insights for future research and development in this field.
基金financially supported by the Fundamental Research Funds for the Central Universities(DUT20RC(3)076)Natural Science Foundation of Liaoning Province(2020-MS-293).Thanks Shuoqi Sun from HZWTECH for help and discussions regarding this study.
文摘We compared a range of BODIPY dimer derivatives without installing blocking groups by optimizing geometry structures and analyzing energies,frontier mo-lecular orbitals,Chole&Cele map,electron density difference,spin-orbit coupling(SOC)matrix and decay rate constants from excited states.The dihedral angles of theβ-β-linked BODIPY dimer and theα-α-linked BODIPY dimer tend to flatten in the T_(1)state,which is detrimental to the occurrence of the intersystem crossing(ISC).Conversely,the dihedral angle of the meso-β-linked BODIPY dimer,the meso-meso-linked BODIPY dimer andα-γ-linked BODIPY dimer is within the range of 125°-143°in the T_(1)state,facilitating ISC and the generation of singlet oxygen.Notably,the transition from S1 to S0 involving lowest unoccupied mo-lecular orbital to highest occupied molecular orbital with long-wavelength emis-sion and moderate oscillator strength underpins the remarkable long emission peaks observed experimentally forα-γ-linked BODIPY dimer.Moreover,the apparent SOC matrix enhances the ISC process,resulting in a respectable effi-ciency in generating singlet oxygen for this dimer.In meso-β-linked BODIPY,meso-meso-linked BODIPY,andα-γ-linked BODIPY,the S_(1)→T_(1)process is characterized by a significant charge transfer,specifically transitioning from the^(1)CT state to the^(3)LE state,indicative of a spin-orbit charge transfer ISC(SOCTISC)mechanism.The ability to regulate the photosensitivity of BODIPY dimers by adjusting the dihedral angle between the two units in the T_(1)state unveils new avenues for designing high-performance photosensitizers for both therapeutic and imaging applications.
基金the financial support of the National Natural Science Foundation of China(No.22168009)。
文摘Highly toxic phosgene,diethyl chlorophosphate(DCP)and volatile acyl chlorides endanger our life and public security.To achieve facile sensing and discrimination of multiple target analytes,herein,we presented a single fluorescent probe(BDP-CHD)for high-throughput screening of phosgene,DCP and volatile acyl chlorides.The probe underwent a covalent cascade reaction with phosgene to form boron dipyrromethene(BODIPY)with bright green fluorescence.By contrast,DCP,diphosgene and acyl chlorides can covalently assembled with the probe,giving rise to strong blue fluorescence.The probe has demonstrated high-throughput detection capability,high sensitivity,fast response(within 3 s)and parts per trillion(ppt)level detection limit.Furthermore,a portable platform based on BDP-CHD was constructed,which has achieved high-throughput discrimination of 16 analytes through linear discriminant analysis(LDA).Moreover,a smartphone adaptable RGB recognition pattern was established for the quantitative detection of multi-analytes.Therefore,this portable fluorescence sensing platform can serve as a versatile tool for rapid and high-throughput detection of toxic phosgene,DCP and volatile acyl chlorides.The proposed“one for more”strategy simplifies multi-target discrimination procedures and holds great promise for various sensing applications.
