The currently reported axial chiral molecules based on the 3,3'-substitution of the binaphthyl skeleton are limited by intrinsic fluorescence properties,resulting in generally low device efficiencies(EQE<5%)of ...The currently reported axial chiral molecules based on the 3,3'-substitution of the binaphthyl skeleton are limited by intrinsic fluorescence properties,resulting in generally low device efficiencies(EQE<5%)of related organic light emitting diodes(OLEDs).Herein,we designed and synthesized four pair of chiral binaphthyl enantiomers(R/S-1-R/S-4)adopting acceptor-donor-donor-acceptor(ADDA)structure by introducing different thioxanthone modification groups on the 3,3'-position of 2,2'-dimethoxy-1,1'-binaphthalene.Among them,emitter R/S-2 and R/S-4 obtained by enhancing intramolecular charge transfer exhibited TADF characteristics due to relatively small Est of 0.12eV and 0.17eV,and relatively moderate SOC matrix elements of 0.28 cm^(-1)and 0.10 cm^(-1)between the 1CT and 3LE states.The CD spectra of these enantiomers in diluted solutions showed perfect mirror images and reasonable gabs for small organic molecules(10^(-4)-10^(-3)).And the external quantum eficiencies(EQE)of 10.9%and 8.32%for device A and B based on emitter S-2 and S-4 were highest compared with currently reported axial chiral molecules based on the 3,3'-position substitution of binaphthyl skeleton,providing simple molecular design strategies to construct efficient CP-OLED device.展开更多
Developing efficient and long wavelength sensitive unimolecular photoinitiators(PIs)is still facing a great challenge.In this work,a series of thioxanthone-based N-hydroxyphthalimide esters(TX-NHPIEs)were synthesized ...Developing efficient and long wavelength sensitive unimolecular photoinitiators(PIs)is still facing a great challenge.In this work,a series of thioxanthone-based N-hydroxyphthalimide esters(TX-NHPIEs)were synthesized by installing NHPIEs along the TX backbone and characterized.The investigated TX-NHPIEs have a 60 nm redshift and demonstrate sterling initiating efficiency for free radical photopolymerization(FRP)under LED@450 nm light irradiation compared with the commercialized isopropylthioxanthone(ITX).Real-time1Hnuclear magnetic resonance(1H NMR),electron spin resonance(ESR),decarboxylation and gas chromatograph-mass spectrometer(GC–MS)experiments and density functional theory(DFT)reveal that TX-NHPIEs can generate one alkyl radical and one N-centered iminyl radical,which can initiate FRP directly and indirectly,respectively.In other words,TX-NHPIEs absorb one photon and can generate two active radicals,which break through the limitations of common PIs.TX-NHPIE-Cpe demonstrates the highest initiating efficiency,and its application in coatings and 3D printing was also studied,indicating TX-NHPIEs have broad potential applications in photopolymerization processes.展开更多
Radiotherapy is an important treatment for cancer,but it is associated with major side effects due to the high dose of radiation(generally more than 50 Gy).Because radiation's low acute and late toxicity,many tumo...Radiotherapy is an important treatment for cancer,but it is associated with major side effects due to the high dose of radiation(generally more than 50 Gy).Because radiation's low acute and late toxicity,many tumors are treated with fractionated radiation in small doses(<2 Gy).Scintillator X-ray-induced photodynamic therapy is an efficient methodology for cancer management that employs small doses of X-ray irradiation(<2 Gy)in a complex process.Here we screened pharmaceutical drug intermediates that are derivatives of thioxanthone(TX)and investigated TX-derived organic pharmaceutical molecules that efficiently undergo X-ray-sensitization to populate triplet excitons(singlet oxygen)for cancer therapy when exposed to low-dose X-ray irradiation.By modifying alkoxy side chain substitutions at the 2-position to tune the molecular packing and intermolecular interactions,the fluorescence and room-temperature phosphorescence of a series of TX derivatives were assessed under X-ray irradiation.The ability of these derivatives to generate singlet oxygen and their potential for treating tumors provide new opportunities for developing organic molecules with simple chemical structures,in which large numbers of triplets can be populated directly under ultralow-dose X-ray irradiation.展开更多
基金funded by National Natural Science Foundation of China(No.21772209)International Partnership Program of Chinese Academy of Sciences(IPP)(No.1A1111KYSB20210028)National Program for Support of Top-notch Young Professionals.
文摘The currently reported axial chiral molecules based on the 3,3'-substitution of the binaphthyl skeleton are limited by intrinsic fluorescence properties,resulting in generally low device efficiencies(EQE<5%)of related organic light emitting diodes(OLEDs).Herein,we designed and synthesized four pair of chiral binaphthyl enantiomers(R/S-1-R/S-4)adopting acceptor-donor-donor-acceptor(ADDA)structure by introducing different thioxanthone modification groups on the 3,3'-position of 2,2'-dimethoxy-1,1'-binaphthalene.Among them,emitter R/S-2 and R/S-4 obtained by enhancing intramolecular charge transfer exhibited TADF characteristics due to relatively small Est of 0.12eV and 0.17eV,and relatively moderate SOC matrix elements of 0.28 cm^(-1)and 0.10 cm^(-1)between the 1CT and 3LE states.The CD spectra of these enantiomers in diluted solutions showed perfect mirror images and reasonable gabs for small organic molecules(10^(-4)-10^(-3)).And the external quantum eficiencies(EQE)of 10.9%and 8.32%for device A and B based on emitter S-2 and S-4 were highest compared with currently reported axial chiral molecules based on the 3,3'-position substitution of binaphthyl skeleton,providing simple molecular design strategies to construct efficient CP-OLED device.
基金the financial support by the National Natural Science Foundation of China(Nos.22301107,52373057)the Nature Science Foundation of Jiangsu Province(No.BK20200610)+1 种基金the Fundamental Research Funds for the Central Universities(No.JUSRP122021)Jiangsu Province"Innovation and Entrepreneurship Doctor"Talent Plan(No.JSSCBS20221053)also provided support。
文摘Developing efficient and long wavelength sensitive unimolecular photoinitiators(PIs)is still facing a great challenge.In this work,a series of thioxanthone-based N-hydroxyphthalimide esters(TX-NHPIEs)were synthesized by installing NHPIEs along the TX backbone and characterized.The investigated TX-NHPIEs have a 60 nm redshift and demonstrate sterling initiating efficiency for free radical photopolymerization(FRP)under LED@450 nm light irradiation compared with the commercialized isopropylthioxanthone(ITX).Real-time1Hnuclear magnetic resonance(1H NMR),electron spin resonance(ESR),decarboxylation and gas chromatograph-mass spectrometer(GC–MS)experiments and density functional theory(DFT)reveal that TX-NHPIEs can generate one alkyl radical and one N-centered iminyl radical,which can initiate FRP directly and indirectly,respectively.In other words,TX-NHPIEs absorb one photon and can generate two active radicals,which break through the limitations of common PIs.TX-NHPIE-Cpe demonstrates the highest initiating efficiency,and its application in coatings and 3D printing was also studied,indicating TX-NHPIEs have broad potential applications in photopolymerization processes.
基金supported by the National Natural Science Foundation of China(82172007,81771977,52103209,and 52373183)the Science Fund for Distinguished Young Scholars of Fujian Province(2021J06007)+2 种基金the Scientific Research Foundation of Xiang An Biomedicine Laboratory(2023XAKJ0101023)the Open Research Fund of the National Facility for Translational Medicine(Shanghai)(TMSK-2021-102)the Open Project of State Key Laboratory of Supramolecular Structure and Materials(sklssm2023026)。
文摘Radiotherapy is an important treatment for cancer,but it is associated with major side effects due to the high dose of radiation(generally more than 50 Gy).Because radiation's low acute and late toxicity,many tumors are treated with fractionated radiation in small doses(<2 Gy).Scintillator X-ray-induced photodynamic therapy is an efficient methodology for cancer management that employs small doses of X-ray irradiation(<2 Gy)in a complex process.Here we screened pharmaceutical drug intermediates that are derivatives of thioxanthone(TX)and investigated TX-derived organic pharmaceutical molecules that efficiently undergo X-ray-sensitization to populate triplet excitons(singlet oxygen)for cancer therapy when exposed to low-dose X-ray irradiation.By modifying alkoxy side chain substitutions at the 2-position to tune the molecular packing and intermolecular interactions,the fluorescence and room-temperature phosphorescence of a series of TX derivatives were assessed under X-ray irradiation.The ability of these derivatives to generate singlet oxygen and their potential for treating tumors provide new opportunities for developing organic molecules with simple chemical structures,in which large numbers of triplets can be populated directly under ultralow-dose X-ray irradiation.
