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
Hyperfluorescent organic light-emitting diodes(HF-OLEDs)approach has made it possible to achieve excellent device performance and color purity with low roll-off using noble-metal-free pure organic emitter.Despite sign...Hyperfluorescent organic light-emitting diodes(HF-OLEDs)approach has made it possible to achieve excellent device performance and color purity with low roll-off using noble-metal-free pure organic emitter.Despite significant progress,the performance of HF-OLEDs is still unsatisfactory due to the existence of a competitive dexter energy transfer(DET)pathway.In this contribution,two boron dipyrromethene(BODIPY)-based donor-acceptor emitters(BDP-C-Cz and BDP-N-Cz)with hybridized local and charge transfer characteristics(HLCT)are introduced in the HF-OLED to suppress the exciton loss by dexter mechanism,and a breakthrough performance with low-efficiency roll-off(0.3%)even at high brightness(1000 cd m^(-2))is achieved.It is demonstrated that the energy loss via the DET channel can be suppressed in HF-OLEDs utilizing the HLCT emitter,as the excitons from the dark triplet state of such emitters are funneled to its emissive singlet state following the hot-exciton mechanism.The developed HF-OLED device has realized a good maximum external quantum efficiency(EQE)of 19.25%at brightness of 1000 cd m^(-2)and maximum luminance over 60000 cd m^(-2),with an emission peak at 602 nm and Commission International de L'Eclairage(CIE)coordinates(0.57,0.41),which is among the best-achieved results in solution-processed HF-OLEDs.This work presents a viable methodology to suppress energy loss and achieve high performance in the HF-OLEDs.展开更多
In this study,diodo boron dipyrromethene(BODIPY)is employed a8 the energy donor and 3,4,9,10-perylene tetracarboxylic dianhydride(PDA)as the energy acceptor,enabling the synthesis of two new compounds:a BODIPY-perylen...In this study,diodo boron dipyrromethene(BODIPY)is employed a8 the energy donor and 3,4,9,10-perylene tetracarboxylic dianhydride(PDA)as the energy acceptor,enabling the synthesis of two new compounds:a BODIPY-perylene dyad named P1,and a triad named P2.To investigate the impact of the energy donor on the photophysical processes of the system,P1 comprises one diodo-BODIPY unit and one PDA unit,whereas P2 contains two diodo-BODIPY moieties and one PDA unit.Due to the good spectral complementarity between diiodo-BODIPY and PDA,these two compounds exhibit excellent light-harvesting capabilities in the 400-620 nm range.Steady-state fluorescence spectra demonstrate that when preferentially exciting the diodo-BODIPY moiety,it can effectively transfer energy to PDA;when selectively exciting the PDA moiety,quenching of PDA fluorescence is observed in both P1 and P2.Nanosecond transient absorption results show that both compounds can efficiently generate triplet excited states,which are located on the PDA part.The lifetimes of the triplet states for these two compounds are 103 and 89μs,respectively,significantly longer than that of diiodo-BODIPY.The results from the photooxidation experiments reveal that both P1 and P2 demonstrate good photostability and photooxidation capabilities,with P2 showing superior photooxidative efficiency.The photooxidation rate constant for P2 is 1.3 times that of P1,and its singlet oxygen quantum yield is 1.6 times that of P1.The results obtained here offer valuable insights for designing new photosensitizers.展开更多
The aggregation-caused quenching(ACQ)rationale has been employed to improve the fluorescence imaging accuracy of nanocarriers by precluding free probe-derived interferences.However,its usefulness is undermined by limi...The aggregation-caused quenching(ACQ)rationale has been employed to improve the fluorescence imaging accuracy of nanocarriers by precluding free probe-derived interferences.However,its usefulness is undermined by limited penetration and low spatiotemporal resolution of NIR-Ⅰ(700-900 nm)bioimaging owing to absorption and diffraction by biological tissues and tissue-derived autofluorescence.This study aimed to develop ACQ-based NIR-Ⅱ(1000-1700 nm)probes to further improve the imaging resolution and accuracy.The strategy employed is to install highly planar and electron-rich julolidine into the 3,5-position of aza-BODIPY based on the larger substituent effects.The newly developed probes displayed remarkable photophysical properties,with intense absorption centered at approximately 850 nm and bright emission in the 950-1300 nm region.Compared with the NIR-Ⅰ counterpart P2,the NIR-Ⅱ probes demonstrated superior water sensitivity and quenching stability.ACQ1 and ACQ6 exhibited more promising ACQ effects with absolute fluorescence quenching at water fractions above 40% and higher quenching stability with less than 2.0% fluorescence reillumination in plasma after 24 h of incubation.Theoretical calculations verified that molecular planarity is more important than hydrophobicity for ACQ properties.Additionally,in vivo and ex vivo reillumination studies revealed less than 2.5% signal interference from prequenched ACQ1,in contrast to 15% for P2.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 Guangdong Foundation of Basic and Applied Basic Research(2019B1515120023,2022B1515020041)National Natural Science Foundation of China(21975053,21975055,U2001222)for financial support
文摘Hyperfluorescent organic light-emitting diodes(HF-OLEDs)approach has made it possible to achieve excellent device performance and color purity with low roll-off using noble-metal-free pure organic emitter.Despite significant progress,the performance of HF-OLEDs is still unsatisfactory due to the existence of a competitive dexter energy transfer(DET)pathway.In this contribution,two boron dipyrromethene(BODIPY)-based donor-acceptor emitters(BDP-C-Cz and BDP-N-Cz)with hybridized local and charge transfer characteristics(HLCT)are introduced in the HF-OLED to suppress the exciton loss by dexter mechanism,and a breakthrough performance with low-efficiency roll-off(0.3%)even at high brightness(1000 cd m^(-2))is achieved.It is demonstrated that the energy loss via the DET channel can be suppressed in HF-OLEDs utilizing the HLCT emitter,as the excitons from the dark triplet state of such emitters are funneled to its emissive singlet state following the hot-exciton mechanism.The developed HF-OLED device has realized a good maximum external quantum efficiency(EQE)of 19.25%at brightness of 1000 cd m^(-2)and maximum luminance over 60000 cd m^(-2),with an emission peak at 602 nm and Commission International de L'Eclairage(CIE)coordinates(0.57,0.41),which is among the best-achieved results in solution-processed HF-OLEDs.This work presents a viable methodology to suppress energy loss and achieve high performance in the HF-OLEDs.
基金supported by the Research Project for Outstanding Young People in Universities of Anhui Province(No.2023AH030099)the China Postdoctoral Science Foundation(No.2023M733378)+3 种基金the National Natural Science Foundation of China(No.21702042,No.22305059,No.22103010)the National University Students'Innovation and Entrepreneurship Training Program(No.202311059024)the Anhui Provincial Natural Science Foundation(No.2308085QB59)the Anhui Provincial Excellent Scientific Research and Innovation Team(No.2022AH010096).
文摘In this study,diodo boron dipyrromethene(BODIPY)is employed a8 the energy donor and 3,4,9,10-perylene tetracarboxylic dianhydride(PDA)as the energy acceptor,enabling the synthesis of two new compounds:a BODIPY-perylene dyad named P1,and a triad named P2.To investigate the impact of the energy donor on the photophysical processes of the system,P1 comprises one diodo-BODIPY unit and one PDA unit,whereas P2 contains two diodo-BODIPY moieties and one PDA unit.Due to the good spectral complementarity between diiodo-BODIPY and PDA,these two compounds exhibit excellent light-harvesting capabilities in the 400-620 nm range.Steady-state fluorescence spectra demonstrate that when preferentially exciting the diodo-BODIPY moiety,it can effectively transfer energy to PDA;when selectively exciting the PDA moiety,quenching of PDA fluorescence is observed in both P1 and P2.Nanosecond transient absorption results show that both compounds can efficiently generate triplet excited states,which are located on the PDA part.The lifetimes of the triplet states for these two compounds are 103 and 89μs,respectively,significantly longer than that of diiodo-BODIPY.The results from the photooxidation experiments reveal that both P1 and P2 demonstrate good photostability and photooxidation capabilities,with P2 showing superior photooxidative efficiency.The photooxidation rate constant for P2 is 1.3 times that of P1,and its singlet oxygen quantum yield is 1.6 times that of P1.The results obtained here offer valuable insights for designing new photosensitizers.
基金supported by the National Natural Science Foundation of China(Nos.82273867 and 82030107)the Science and Technology Commission of Shanghai Municipality(No.21430760800,China).
文摘The aggregation-caused quenching(ACQ)rationale has been employed to improve the fluorescence imaging accuracy of nanocarriers by precluding free probe-derived interferences.However,its usefulness is undermined by limited penetration and low spatiotemporal resolution of NIR-Ⅰ(700-900 nm)bioimaging owing to absorption and diffraction by biological tissues and tissue-derived autofluorescence.This study aimed to develop ACQ-based NIR-Ⅱ(1000-1700 nm)probes to further improve the imaging resolution and accuracy.The strategy employed is to install highly planar and electron-rich julolidine into the 3,5-position of aza-BODIPY based on the larger substituent effects.The newly developed probes displayed remarkable photophysical properties,with intense absorption centered at approximately 850 nm and bright emission in the 950-1300 nm region.Compared with the NIR-Ⅰ counterpart P2,the NIR-Ⅱ probes demonstrated superior water sensitivity and quenching stability.ACQ1 and ACQ6 exhibited more promising ACQ effects with absolute fluorescence quenching at water fractions above 40% and higher quenching stability with less than 2.0% fluorescence reillumination in plasma after 24 h of incubation.Theoretical calculations verified that molecular planarity is more important than hydrophobicity for ACQ properties.Additionally,in vivo and ex vivo reillumination studies revealed less than 2.5% signal interference from prequenched ACQ1,in contrast to 15% for P2.
