Herein,we disclose a novel copper-catalyzed C(sp)-H aryl amination of terminal alkynes with anthranils,enabling the rapid generation of highly reactive secondary N-aryl ynamines for the modular synthesis of structural...Herein,we disclose a novel copper-catalyzed C(sp)-H aryl amination of terminal alkynes with anthranils,enabling the rapid generation of highly reactive secondary N-aryl ynamines for the modular synthesis of structurally diverse C2-substituted quinolines and 2-quinolinones.The in-situ formed carbonyl-ynamines are prone to tautomerize to carbonyl-ketenimines,which can efficiently react with a series of nucleophiles,including amines,alcohols,phenols,thiols,thiophenols,active-methylene compounds,and even water to produce various quinoline derivatives with the generation of H_(2)O as a sole and green byproduct.This method also unlocks a practical route to create various quinoline-fused heterocycles and can be successfully applied to the late-stage modification of complex molecules and the concise synthesis of bioactive targets.Mechanistic studies reveal a coppercatalyzed inner-sphere nitrene transfer process by using anthranils as novel aryl nitrene precursors.展开更多
By employing the asymmetric end-group engineering,an asymmetric nonfused-ring electron acceptor(NFREA)was designed and synthesized.Compared with the symmetric analogs(NoCA-17 and NoCA-18),NoCA-19 possesses broader lig...By employing the asymmetric end-group engineering,an asymmetric nonfused-ring electron acceptor(NFREA)was designed and synthesized.Compared with the symmetric analogs(NoCA-17 and NoCA-18),NoCA-19 possesses broader light absorption range,more coplanarπ-conjugated backbone,and appropriate crystallinity according to the experimental and theoretical results.The organic solar cells based on J52:NoCA-19 exhibited a power conversion efficiency as high as 12.26%,which is much higher than those of J52:NoCA-17(9.50%)and J52:NoCA-18(11.77%),mainly due to more efficient exciton dissociation,better and balanced charge mobility,suppressed recombination loss,shorter charge extraction time,longer charge carrier lifetimes,and more favorable blend film morphology.These findings demonstrate the great potential of asymmetric end-group engineering in exploring low-cost and high-performance NFREAs.展开更多
Triplet-triplet annihilation(TTA) upconversion-based materials have potential application in the broad range of research areas, including photocatalysis and life sciences. However, near-infrared(NIR)-to-blue upconvert...Triplet-triplet annihilation(TTA) upconversion-based materials have potential application in the broad range of research areas, including photocatalysis and life sciences. However, near-infrared(NIR)-to-blue upconverted emission is preferred for most of the practical applications, but developing a NIR-to-blue TTA upconversion system is a challenging task in photochemistry. In this work, a thermally activated delayed fluorescence(TADF) material with intense visible-to-NIR absorption is demonstrated that shows a longer triplet state lifetime(32 μs) and high triplet state energy(E_(T)= 1.55 e V). For the first time, a heavy atomfree NIR(λ_(ex)> 650 nm) to blue(λ_(em)< 460 nm) TTA upconversion system was devised, employing the dimeric borondifluoride curcuminoid TADF material as triplet photosensitizer(PS) and a large anti-Stokes shift(0.88 e V) along with moderate upconversion yield was achieved. Our work provides the solution and guidance for the future development of purely organic heavy atom-free NIR activating TTA upconversion system for a wide array of applications.展开更多
Three new deep blue light emitters,bearing quinoxaline with different substituents(biphenyl/pyrene)at the 1-or 2-position,were synthesized by a Pd-catalysed coupling reaction in high yields,and were fully characterize...Three new deep blue light emitters,bearing quinoxaline with different substituents(biphenyl/pyrene)at the 1-or 2-position,were synthesized by a Pd-catalysed coupling reaction in high yields,and were fully characterized by 1H/13C NMR spectroscopy,single crystal X-ray diffraction,and high-resolution mass spectrometry(HRMS).展开更多
Artificial membrane transporters that either use chalcogen bonds to facilitate transmembrane flux of anions or show high selectivity toward perchlorate anions are rare.In this work,we report on one such novel monopept...Artificial membrane transporters that either use chalcogen bonds to facilitate transmembrane flux of anions or show high selectivity toward perchlorate anions are rare.In this work,we report on one such novel monopeptide-based transporter system,featuring both chalcogen bonds for highly efficient anion transport and high transport selectivity toward ClO_(4)^(-) anions.Structurally,these monopeptide molecules associate with each other via H-bonds to produce H-bonded 1D stack that not only one dimensionally but also directionally aligns the terminal bicyclic thiophene motifs to the same side.Functionally,these well-aligned thiophenes create a sulfur-rich transmembrane pathway,combinatorially fine-tunable to enable anions to efficiently cross the membrane in the increasing activity of Cl^(-)<Br^(-)<NO_(3)^(-)<ClO_(4)^(-) via chalcogen bonds,with EC_(50)values of 0.75,0.40,0.37 and 0.093μmol/L(0.3 mol%relative to lipid molecules),respectively.展开更多
基金supported by the National Natural Science Foundation of China (22271065,22271314)the Guangzhou Basic and Applied Research (202201010396)。
文摘Herein,we disclose a novel copper-catalyzed C(sp)-H aryl amination of terminal alkynes with anthranils,enabling the rapid generation of highly reactive secondary N-aryl ynamines for the modular synthesis of structurally diverse C2-substituted quinolines and 2-quinolinones.The in-situ formed carbonyl-ynamines are prone to tautomerize to carbonyl-ketenimines,which can efficiently react with a series of nucleophiles,including amines,alcohols,phenols,thiols,thiophenols,active-methylene compounds,and even water to produce various quinoline derivatives with the generation of H_(2)O as a sole and green byproduct.This method also unlocks a practical route to create various quinoline-fused heterocycles and can be successfully applied to the late-stage modification of complex molecules and the concise synthesis of bioactive targets.Mechanistic studies reveal a coppercatalyzed inner-sphere nitrene transfer process by using anthranils as novel aryl nitrene precursors.
基金the financial support fromtheNSFC(21975055,U2001222,52103352,52120105006,and 51925306)National Key R&D Program of China(2018FYA 0305800)+2 种基金Key Research Program of Chinese Academy of Sciences(XDPB08-2)the Youth Innovation Promotion Association of Chinese Academy of Sciences(2022165)the Fundamental Research Funds for the Central Universities.DFT results described in this article were obtained from the National Supercomputing Centre in Shenzhen(Shenzhen Cloud Computing Centre).
文摘By employing the asymmetric end-group engineering,an asymmetric nonfused-ring electron acceptor(NFREA)was designed and synthesized.Compared with the symmetric analogs(NoCA-17 and NoCA-18),NoCA-19 possesses broader light absorption range,more coplanarπ-conjugated backbone,and appropriate crystallinity according to the experimental and theoretical results.The organic solar cells based on J52:NoCA-19 exhibited a power conversion efficiency as high as 12.26%,which is much higher than those of J52:NoCA-17(9.50%)and J52:NoCA-18(11.77%),mainly due to more efficient exciton dissociation,better and balanced charge mobility,suppressed recombination loss,shorter charge extraction time,longer charge carrier lifetimes,and more favorable blend film morphology.These findings demonstrate the great potential of asymmetric end-group engineering in exploring low-cost and high-performance NFREAs.
基金the National Natural Science Foundation of China (Nos. 21975053, 21975055, U2001222)Guangdong Basic and Applied Basic Research Foundation (Nos. 2019B1515120023, 2022B1515020041)Guangdong Province Universities and Colleges Pearl River Scholar Funded Scheme (2019) for financial support。
文摘Triplet-triplet annihilation(TTA) upconversion-based materials have potential application in the broad range of research areas, including photocatalysis and life sciences. However, near-infrared(NIR)-to-blue upconverted emission is preferred for most of the practical applications, but developing a NIR-to-blue TTA upconversion system is a challenging task in photochemistry. In this work, a thermally activated delayed fluorescence(TADF) material with intense visible-to-NIR absorption is demonstrated that shows a longer triplet state lifetime(32 μs) and high triplet state energy(E_(T)= 1.55 e V). For the first time, a heavy atomfree NIR(λ_(ex)> 650 nm) to blue(λ_(em)< 460 nm) TTA upconversion system was devised, employing the dimeric borondifluoride curcuminoid TADF material as triplet photosensitizer(PS) and a large anti-Stokes shift(0.88 e V) along with moderate upconversion yield was achieved. Our work provides the solution and guidance for the future development of purely organic heavy atom-free NIR activating TTA upconversion system for a wide array of applications.
基金This work was supported by the National Natural Science Foundation of China(Nos.21975054 and 21602014)the Natural Science Foundation of Guangdong Provinee of China(No.2019A1515010925)+2 种基金the Guangdong Provincial Key Laboratory of Information Photonics Technology(No.2020B121201011)the"One Hundred Talents Program"of the Guangdong University of Technology(No.1108-220413205)the Guangdong Provincial Key Laboratory of Functional Soft Condensed Matter of The Guang-dong University of Technology(No.220413205).
文摘Three new deep blue light emitters,bearing quinoxaline with different substituents(biphenyl/pyrene)at the 1-or 2-position,were synthesized by a Pd-catalysed coupling reaction in high yields,and were fully characterized by 1H/13C NMR spectroscopy,single crystal X-ray diffraction,and high-resolution mass spectrometry(HRMS).
基金supported by the construct program of applied characteristic discipline in Hunan University of Science and Engineering,the Technology Plan of Guangdong Province(No. 2019A050510042)the Natural Science Foundation of Hunan Province of China (No. 2021JJ30291)Northwestern Polytechnical University。
文摘Artificial membrane transporters that either use chalcogen bonds to facilitate transmembrane flux of anions or show high selectivity toward perchlorate anions are rare.In this work,we report on one such novel monopeptide-based transporter system,featuring both chalcogen bonds for highly efficient anion transport and high transport selectivity toward ClO_(4)^(-) anions.Structurally,these monopeptide molecules associate with each other via H-bonds to produce H-bonded 1D stack that not only one dimensionally but also directionally aligns the terminal bicyclic thiophene motifs to the same side.Functionally,these well-aligned thiophenes create a sulfur-rich transmembrane pathway,combinatorially fine-tunable to enable anions to efficiently cross the membrane in the increasing activity of Cl^(-)<Br^(-)<NO_(3)^(-)<ClO_(4)^(-) via chalcogen bonds,with EC_(50)values of 0.75,0.40,0.37 and 0.093μmol/L(0.3 mol%relative to lipid molecules),respectively.
