The excited state dynamics and critically regulated factors of reverse intersystem crossing(RISC)in through-space charge transfer(TSCT)molecules have received insufficient attention.Here,five molecules of through spac...The excited state dynamics and critically regulated factors of reverse intersystem crossing(RISC)in through-space charge transfer(TSCT)molecules have received insufficient attention.Here,five molecules of through space/bond charge transfer inducing thermally activated delayed fluorescence(TADF)are prepared,and their excited state charge transfer processes are studied by ultrafast transient absorption and theoretical calculations.DM-Z has a largerΔEST,leading to a longer lifetime of intersystem crossing(ISC),resulting in the lowest photoluminescence quantum yield(PLQY).Oppositely,ISC and RISC are demonstrated to take place with shorter lifetimes for TSCT molecules.The face-to-faceπ-πstacking interactions and electron communication enable DM-B and DM-BX to have an efficient RISC,increasing the weight coefficient of RISC from 1.7%(DM-X)to close to 50%(DM-B and DM-BX)in the solvents,which make DM-BX and DM-B to have a high PLQY.However,partial local excitation in the donor center is observed and the charge transfer is decreased for DM-G and DM-X.The triplet excited state(DM-G)or singlet excited state(DM-X)mainly undergoes inactivation through a non-radiative relaxation process,resulting in less RISC and low PLQY.This work provides theoretical hints to enhance the RISC process in the TADF materials.展开更多
The development of circularly polarized luminescence(CPL)materials with high performance is signifi-cantly important.Herein,we develop a facial strategy for fabricating a CPL-active system by employing an achiral lumi...The development of circularly polarized luminescence(CPL)materials with high performance is signifi-cantly important.Herein,we develop a facial strategy for fabricating a CPL-active system by employing an achiral luminescent metal-organic cage(MOC)and chiral boron dipyrromethene(BODIPY)molecules.CPL is achieved by taking advantage of the radiative energy transfer process,in which BODIPY molecules act as energy acceptors and MOCs act as donors.The CPL performance(maximum luminescence dissymme-try factor up to±1.5×10^(−3))can be tuned by adjusting the ratio between MOCs and BODIPY.White-light emission with the CPL feature is obtained by using a ternary system including MOC,chiral BODIPY,and Rhodamine B.The present work provides a facile and universal strategy to construct a CPL-active system by integrating achiral luminophores and chiral molecules.展开更多
Herein,we report the facile synthesis of a highly strained hexabenzocoronene-containing carbon nanoring,cyclo[4]-paraphenylene[2]-2,11-hexabenzocoronenylene([4,2]CPHBC),as the segment of a[10,10]single-walled carbon n...Herein,we report the facile synthesis of a highly strained hexabenzocoronene-containing carbon nanoring,cyclo[4]-paraphenylene[2]-2,11-hexabenzocoronenylene([4,2]CPHBC),as the segment of a[10,10]single-walled carbon nanotube([10,10]SWNT).[4,2]CPHBC was synthesized based on the platinummediated assembly of diborylbiphenyl and diborylhexabenzocoronene,forming a tetranuclear platinum complex,followed by reductive elimination.This nanoring molecule was confirmed by NMR and HRMS,and its photophysical properties were studied using steady-state and time-resolved spectroscopies.Moreover,the selective supramolecular host-vip interaction between[4,2]CPHBC and C_(60) was also investigated.展开更多
The synthesis of helical nanostructures with advanced functions from atomically precise building blocks is attractive,but remains a significant challenge.In this work,we report two atomically precise metal hydride clu...The synthesis of helical nanostructures with advanced functions from atomically precise building blocks is attractive,but remains a significant challenge.In this work,we report two atomically precise metal hydride clusters,Cu_(24)H_(6)L_(12)(PPh_(3))_(2)Pz_(6)(Cu@Cu_(23)H_(6),)and Cu_(24-x)AgxH_(6)L_(12)(PPh_(3))_(2)Pz_(6)(0<x<1)(Ag@Cu_(23)H_(6))(L=CH3 OPhC≡C−,Pz=3,5-(CF_(3))_(2)-pyrazolate),containing M@Cu_(23)(M=Cu/Ag)kernels with D_(3)-symmetry.Single crystal X-ray diffraction results reveal that the DNA-like double-helical nanostructures driven by intrastrand and interstrand supramolecular interactions,including weak hydrogen bonds(i.e.,C–H···F/O/C)and van der Waal’s interactions(i.e.,C···F and F···F),are formed through the self-hierarchical assembly of Cu@Cu_(23)H_(6)and Ag@Cu_(23)H_(6).In addition,Cu@Cu_(23)H_(6)is nonemissive.After doping with Ag,Ag@Cu_(23)H_(6)exhibits thermally activated delayed fluorescence(TADF)both in the solid state and in solution,which was seldom presented in high-nuclear clusters.Experimental and theoretical calculations suggest that the efficient separation of highest occupied molecular orbital and lowest unoccupied molecular orbital as well as larger spin–orbit coupling of Ag@Cu_(23)H_(6)than Cu@Cu_(23)H_(6)are responsible for the TADF.This work not only provides a platform to facilitate the in-depth investigation of selfhierarchical assembly mechanisms of double-helical nanostructures but also demonstrates that the doping strategy can endow helical nanostructures with interesting luminescent behavior.展开更多
Exploring earth-abundant photosensitizers(PSs)with strong visible light absorption is a long-standing interest,but still challenging.Although copper(Ⅰ)cyclic trinuclear complexes(Cu-CTCs)have exhibited fascinating ph...Exploring earth-abundant photosensitizers(PSs)with strong visible light absorption is a long-standing interest,but still challenging.Although copper(Ⅰ)cyclic trinuclear complexes(Cu-CTCs)have exhibited fascinating photoluminescence properties,their potential application as photosensitizers remains unexplored.Herein,a Cu-CTC(1)bearing boron dipyrromethene(BODIPY)groups was constructed and its photophysical behaviours comprehensively investigated by steady-state spectroscopy,time-resolved transient absorption spectroscopy,and theoretical calculations.The introduction of BODIPY groups in 1 endowed it with a high-lying singlet excited state for strong visible light absorption and long-lived triplet excited states.In addition,highly efficient ISC for populating the long-lived triplet states was achieved by metal-to-ligand charge-transfer(MLCT)singlet and triplet excited states.Cu-CTC without the BODIPY group(2)could not absorb visible light,whereas 1 displayed a high molar extinction coefficient(ε)of 78515 M^(-1) cm^(-1) in the visible light region,which is rarely achieved for Cu-CTCs.Furthermore,1 exhibited much higher photooxidation activity than that of 2,a conventional noble-metal PS(i.e.,Ir(ppy)3)and a well-established Cu(Ⅰ)-PS(i.e.,Cu(phen)2BF4)for both electro-and energy-transfer reactions.Our investigation provides a feasible approach for designing Cu-CTCs as promising photosensitizers.展开更多
Metal-semiconductor plasmonic metasurfaces enable precise optical field manipulation at the subwavelength scale;however,most existing designs rely on external fields and exhibit only binary responses,thereby restricti...Metal-semiconductor plasmonic metasurfaces enable precise optical field manipulation at the subwavelength scale;however,most existing designs rely on external fields and exhibit only binary responses,thereby restricting the realization of multistate logic operations.Here,we present an in-situ polarization-controlled approach based on an Au-indium tin oxide(ITO)bilayer nanocrescent with a Schottky heterojunction for achieving polarization-dependent tristate optical modulation.Polarization-selective excitation of distinct localized plasmon modes facilitates directional hot-electron injection across the Au-ITO interface,thereby producing three distinct programmable states—positive,zero,and negative—at a single detection wavelength.This symmetric bilayer design is applicable to other metal-semiconductor composites and offers generalizable design principles for ternary logic,multistate optical encoding,and ultrafast photonic information processing.The proposed concept is validated through both experimental measurements and numerical simulations.展开更多
Holographic polymer/liquid-crystal composites,which are periodically ordered materials with alternative polymer-rich and liquid-crystal-rich phases, have drawn increasing interest due to their unique capabilities of r...Holographic polymer/liquid-crystal composites,which are periodically ordered materials with alternative polymer-rich and liquid-crystal-rich phases, have drawn increasing interest due to their unique capabilities of reconstructing colored three-dimensional(3 D) images and enabling the electro-optic response. They are formed via photopolymerization induced phase separation upon exposure to laser interference patterns, where a fast photopolymerization is required to facilitate the holographic patterning. Yet, the fast photopolymerization generally leads to depressed phase separation and it remains challenging to boost the holographic performance via kinetics control.Herein, we disclose that the ketyl radical inhibition is able to significantly boost the phase separation and holographic performance by preventing the proliferated diffusion of initiating radicals from the constructive to the destructive regions. Dramatically depressed phase separation is caused when converting the inhibiting ketyl radical to a new initiating radical, indicating the significance of ketyl radical inhibition when designing high performance holographic polymer composites.展开更多
The efficient harvesting of triplet excitons is crucial to the realization of high-performance organic light-emitting diodes(OLEDs).Herein,we show that coordination of donor-acceptor(D-A)type molecules to a metal atom...The efficient harvesting of triplet excitons is crucial to the realization of high-performance organic light-emitting diodes(OLEDs).Herein,we show that coordination of donor-acceptor(D-A)type molecules to a metal atom in a monodentate fashion can lead to thermally activated delayed fluorescence(TADF)emissions with wide color tunability only through varying the noncoordinating acceptor moiety.A panel of TADF gold(Ⅰ)complexes with emission maxima(λmax)of 545–645 nm from metal perturbed intraligand charge-transfer(MPICT)excited states have been developed.Synergetic effects of heavy atom-induced spin-orbit coupling(SOC),steric-induced donor-acceptor twisting and suppressed intramolecular motions lead to high emission efficiencies of 65%-85%in doped films with delayed fluorescence lifetime of as short as 2.0μs.Transient absorption spectroscopic studies on selected complexes determined the kISCto be 6.5×10^(9)s^(-1).Theoretical calculations confirmed the participation of minor d orbital into the lowest excited state,which led to an SOC value of 5.19 cm^(-1)between the lowest-lying singlet and triplet excited states.The yellow to deep red solution-processed OLEDs based on the new gold(Ⅰ)complexes incorporated with various D-A ligands demonstrated promising performances.This study validates a modular design for TADF metal complexes,which will broaden the choices of metal centers and allow for facile color tuning via simple ligand synthesis.展开更多
Plasmon-induced hot energy in metal nanostructures holds great promise for photocatalytic organic conversions.However,maintaining the high-energy state of hot electrons within these structures remains challenging,even...Plasmon-induced hot energy in metal nanostructures holds great promise for photocatalytic organic conversions.However,maintaining the high-energy state of hot electrons within these structures remains challenging,even in hybrid metal-semiconductor heterojunctions.The rapid relaxation of hot electrons(<1 ps)due to a thick-shell and loosely bound semiconductor layer limits their extraction efficiency and utilization effectiveness during photocatalysis.Herein,we fabricated a novel metalsemiconductor heterojunction(P2-Au)with ultrathin-shell semiconductor layer by combing ultra-small metal chalcogenide semiconductor clusters(P2)with gold nanorods(Au NRs),which exhibits high-efficiency extraction of hot electrons and photocatalytic application.The robust binding of P2 cluster,with its smaller volume and larger energy level splitting compared to large-sized quantum dots,not only significantly increases the yield of hot electrons but also enables their rapid extraction and sustains long-lived(>2 ns)high-energy states.As a proof of concept,the composite photocatalyst achieves near-infrared-lightdriven C(sp^(3))-S cross-coupling reactions for the first time.This protocol effectively produces over 50 alkylthioethers from a wide scope range of non-active alkyl bromides and chlorides,aryl and alkyl thiols.This work provides a new strategy for highefficiency extraction of hot electrons within plasmonic metal nanostructures and paves the way for hot electron-driven photocatalytic organic transformations.展开更多
Conductive coordination polymers(CCPs)have shown great potential for electronic purposes.However,their applications in photodetection have been limited by poor sensitivity,low on/off current ratio,and slow response ow...Conductive coordination polymers(CCPs)have shown great potential for electronic purposes.However,their applications in photodetection have been limited by poor sensitivity,low on/off current ratio,and slow response owing to the low charge generation and/or separation efficiency.In this work,metal-to-ligand chargetransfer(MLCT)in PhSeAg was used to fabricate a single-component MLCT photodetecting material for the first time to solve the above challenges.The material obtained possesses ultrahigh sensitivity to weak-light intensity(0.03 mW cm^(−2)),the highest on/off ratio,and the fastest response speed than other wellknown CCPs materials tested.Our work might provide a simple but common strategy for designing high-performance CCPs composites for optoelectrical applications.展开更多
基金supported by the National Natural Science Foundation of China(No.22273057)the Universities Joint Laboratory of Guangdong,Hong Kong and Macao(No.2021LSYS009)+2 种基金the Natural Science Foundation of Guangdong Province(Nos.2022A1515011661,2023A1515012631)the Chemistry and Chemical Engineering Guangdong Laboratory(No.1922003)Guangdong Major Project of Basic and Applied Basic Research(No.2019B030302009)。
文摘The excited state dynamics and critically regulated factors of reverse intersystem crossing(RISC)in through-space charge transfer(TSCT)molecules have received insufficient attention.Here,five molecules of through space/bond charge transfer inducing thermally activated delayed fluorescence(TADF)are prepared,and their excited state charge transfer processes are studied by ultrafast transient absorption and theoretical calculations.DM-Z has a largerΔEST,leading to a longer lifetime of intersystem crossing(ISC),resulting in the lowest photoluminescence quantum yield(PLQY).Oppositely,ISC and RISC are demonstrated to take place with shorter lifetimes for TSCT molecules.The face-to-faceπ-πstacking interactions and electron communication enable DM-B and DM-BX to have an efficient RISC,increasing the weight coefficient of RISC from 1.7%(DM-X)to close to 50%(DM-B and DM-BX)in the solvents,which make DM-BX and DM-B to have a high PLQY.However,partial local excitation in the donor center is observed and the charge transfer is decreased for DM-G and DM-X.The triplet excited state(DM-G)or singlet excited state(DM-X)mainly undergoes inactivation through a non-radiative relaxation process,resulting in less RISC and low PLQY.This work provides theoretical hints to enhance the RISC process in the TADF materials.
基金financially supported by the National Natural Science Foundation of China (Nos.22171106,21731002,21975104,21871172,and 22201101)the Guangdong Major Project of Basic and Applied Research (No.2019B030302009)+4 种基金Guangdong Natural Science Foundation (No.2022A1515011937)the Guangzhou Science and Technology Program (No.202002030411)the China Postdoctoral Science Foundation (No.2022M711327)Guangdong Basic and Applied Basic Research Foundation (No.2022A1515110523)Jinan University
文摘The development of circularly polarized luminescence(CPL)materials with high performance is signifi-cantly important.Herein,we develop a facial strategy for fabricating a CPL-active system by employing an achiral luminescent metal-organic cage(MOC)and chiral boron dipyrromethene(BODIPY)molecules.CPL is achieved by taking advantage of the radiative energy transfer process,in which BODIPY molecules act as energy acceptors and MOCs act as donors.The CPL performance(maximum luminescence dissymme-try factor up to±1.5×10^(−3))can be tuned by adjusting the ratio between MOCs and BODIPY.White-light emission with the CPL feature is obtained by using a ternary system including MOC,chiral BODIPY,and Rhodamine B.The present work provides a facile and universal strategy to construct a CPL-active system by integrating achiral luminophores and chiral molecules.
基金financially supported by the National Natural Science Foundation of China(Nos.22225108,21971229).
文摘Herein,we report the facile synthesis of a highly strained hexabenzocoronene-containing carbon nanoring,cyclo[4]-paraphenylene[2]-2,11-hexabenzocoronenylene([4,2]CPHBC),as the segment of a[10,10]single-walled carbon nanotube([10,10]SWNT).[4,2]CPHBC was synthesized based on the platinummediated assembly of diborylbiphenyl and diborylhexabenzocoronene,forming a tetranuclear platinum complex,followed by reductive elimination.This nanoring molecule was confirmed by NMR and HRMS,and its photophysical properties were studied using steady-state and time-resolved spectroscopies.Moreover,the selective supramolecular host-vip interaction between[4,2]CPHBC and C_(60) was also investigated.
基金financially supported by the National Natural Science Foundation of China(grant nos.22371091,21975104,22150004,and 22101099)Guangdong Basic and Applied Basic Research Foundation(grant no.2024A1515010897)+2 种基金the Guangdong Major Project of Basic and Applied Research(grant no.2019B030302009)the China Postdoctoral Science Foundation(grant nos.2022M711327 and 2023T160269)the Outstanding Innovative Talents Cultivation Funded Programs for Doctoral Students of Jinan University(grant no.2023CXB012).
文摘The synthesis of helical nanostructures with advanced functions from atomically precise building blocks is attractive,but remains a significant challenge.In this work,we report two atomically precise metal hydride clusters,Cu_(24)H_(6)L_(12)(PPh_(3))_(2)Pz_(6)(Cu@Cu_(23)H_(6),)and Cu_(24-x)AgxH_(6)L_(12)(PPh_(3))_(2)Pz_(6)(0<x<1)(Ag@Cu_(23)H_(6))(L=CH3 OPhC≡C−,Pz=3,5-(CF_(3))_(2)-pyrazolate),containing M@Cu_(23)(M=Cu/Ag)kernels with D_(3)-symmetry.Single crystal X-ray diffraction results reveal that the DNA-like double-helical nanostructures driven by intrastrand and interstrand supramolecular interactions,including weak hydrogen bonds(i.e.,C–H···F/O/C)and van der Waal’s interactions(i.e.,C···F and F···F),are formed through the self-hierarchical assembly of Cu@Cu_(23)H_(6)and Ag@Cu_(23)H_(6).In addition,Cu@Cu_(23)H_(6)is nonemissive.After doping with Ag,Ag@Cu_(23)H_(6)exhibits thermally activated delayed fluorescence(TADF)both in the solid state and in solution,which was seldom presented in high-nuclear clusters.Experimental and theoretical calculations suggest that the efficient separation of highest occupied molecular orbital and lowest unoccupied molecular orbital as well as larger spin–orbit coupling of Ag@Cu_(23)H_(6)than Cu@Cu_(23)H_(6)are responsible for the TADF.This work not only provides a platform to facilitate the in-depth investigation of selfhierarchical assembly mechanisms of double-helical nanostructures but also demonstrates that the doping strategy can endow helical nanostructures with interesting luminescent behavior.
基金Guangdong Basic and Applied Basic Research Foundation(no.2019B151502024 and 2021A0505030037)Guangdong Province Pearl River Scholar Funded Scheme(2019)+1 种基金supported financially by the National Natural Science Foundation of China(no.21731002,21975104,22150004 and 21901085)the Guangdong Major Project of Basic and Applied Research(no.2019B030302009).
文摘Exploring earth-abundant photosensitizers(PSs)with strong visible light absorption is a long-standing interest,but still challenging.Although copper(Ⅰ)cyclic trinuclear complexes(Cu-CTCs)have exhibited fascinating photoluminescence properties,their potential application as photosensitizers remains unexplored.Herein,a Cu-CTC(1)bearing boron dipyrromethene(BODIPY)groups was constructed and its photophysical behaviours comprehensively investigated by steady-state spectroscopy,time-resolved transient absorption spectroscopy,and theoretical calculations.The introduction of BODIPY groups in 1 endowed it with a high-lying singlet excited state for strong visible light absorption and long-lived triplet excited states.In addition,highly efficient ISC for populating the long-lived triplet states was achieved by metal-to-ligand charge-transfer(MLCT)singlet and triplet excited states.Cu-CTC without the BODIPY group(2)could not absorb visible light,whereas 1 displayed a high molar extinction coefficient(ε)of 78515 M^(-1) cm^(-1) in the visible light region,which is rarely achieved for Cu-CTCs.Furthermore,1 exhibited much higher photooxidation activity than that of 2,a conventional noble-metal PS(i.e.,Ir(ppy)3)and a well-established Cu(Ⅰ)-PS(i.e.,Cu(phen)2BF4)for both electro-and energy-transfer reactions.Our investigation provides a feasible approach for designing Cu-CTCs as promising photosensitizers.
基金supported by the National Natural Science Foundation of China(Nos.12374345,U24A20103,12404358,and 12304309)the Natural Science Foundation of Zhejiang Province(Nos.LZ26E010002 and LQN25A040010)+2 种基金the Key R&D Project of Zhejiang Province(No.2024C03258)the Fundamental Research Funds for the Provincial Universities of Zhejiang(No.GK259909299001-310)the Hong Kong Joint Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province(No.2023B1212120011).
文摘Metal-semiconductor plasmonic metasurfaces enable precise optical field manipulation at the subwavelength scale;however,most existing designs rely on external fields and exhibit only binary responses,thereby restricting the realization of multistate logic operations.Here,we present an in-situ polarization-controlled approach based on an Au-indium tin oxide(ITO)bilayer nanocrescent with a Schottky heterojunction for achieving polarization-dependent tristate optical modulation.Polarization-selective excitation of distinct localized plasmon modes facilitates directional hot-electron injection across the Au-ITO interface,thereby producing three distinct programmable states—positive,zero,and negative—at a single detection wavelength.This symmetric bilayer design is applicable to other metal-semiconductor composites and offers generalizable design principles for ternary logic,multistate optical encoding,and ultrafast photonic information processing.The proposed concept is validated through both experimental measurements and numerical simulations.
基金financial supports from the National Natural Science Foundation of China (51433002 and 51773073)HUST peak boarding program+1 种基金the National Science Foundation (NSF) of Hubei Scientific Committee (2016CFA001)the Fundamental Research Funds for the Central Universities (2019kfy RCPY089)
文摘Holographic polymer/liquid-crystal composites,which are periodically ordered materials with alternative polymer-rich and liquid-crystal-rich phases, have drawn increasing interest due to their unique capabilities of reconstructing colored three-dimensional(3 D) images and enabling the electro-optic response. They are formed via photopolymerization induced phase separation upon exposure to laser interference patterns, where a fast photopolymerization is required to facilitate the holographic patterning. Yet, the fast photopolymerization generally leads to depressed phase separation and it remains challenging to boost the holographic performance via kinetics control.Herein, we disclose that the ketyl radical inhibition is able to significantly boost the phase separation and holographic performance by preventing the proliferated diffusion of initiating radicals from the constructive to the destructive regions. Dramatically depressed phase separation is caused when converting the inhibiting ketyl radical to a new initiating radical, indicating the significance of ketyl radical inhibition when designing high performance holographic polymer composites.
基金supported by the National Natural Science Foundation of China(22322505,22271196,22301226)the Shenzhen Science and Technology Program(ZDSYS20210623091813040)support from the Department of Science and Technology of Guangdong Province(2019QN01C617)。
文摘The efficient harvesting of triplet excitons is crucial to the realization of high-performance organic light-emitting diodes(OLEDs).Herein,we show that coordination of donor-acceptor(D-A)type molecules to a metal atom in a monodentate fashion can lead to thermally activated delayed fluorescence(TADF)emissions with wide color tunability only through varying the noncoordinating acceptor moiety.A panel of TADF gold(Ⅰ)complexes with emission maxima(λmax)of 545–645 nm from metal perturbed intraligand charge-transfer(MPICT)excited states have been developed.Synergetic effects of heavy atom-induced spin-orbit coupling(SOC),steric-induced donor-acceptor twisting and suppressed intramolecular motions lead to high emission efficiencies of 65%-85%in doped films with delayed fluorescence lifetime of as short as 2.0μs.Transient absorption spectroscopic studies on selected complexes determined the kISCto be 6.5×10^(9)s^(-1).Theoretical calculations confirmed the participation of minor d orbital into the lowest excited state,which led to an SOC value of 5.19 cm^(-1)between the lowest-lying singlet and triplet excited states.The yellow to deep red solution-processed OLEDs based on the new gold(Ⅰ)complexes incorporated with various D-A ligands demonstrated promising performances.This study validates a modular design for TADF metal complexes,which will broaden the choices of metal centers and allow for facile color tuning via simple ligand synthesis.
基金supported by the National Natural Science Foundation of China(U22A20432,92261205,22071165,22201103)the 111 Project(D20015)+2 种基金the Guangzhou Municipal Science and Technology Bureau(2024A04J3490)supported by the State Key Laboratory of Bioactive Molecules and Druggability Assessment(202402025)the Fundamental Research Funds for the Central Universities。
文摘Plasmon-induced hot energy in metal nanostructures holds great promise for photocatalytic organic conversions.However,maintaining the high-energy state of hot electrons within these structures remains challenging,even in hybrid metal-semiconductor heterojunctions.The rapid relaxation of hot electrons(<1 ps)due to a thick-shell and loosely bound semiconductor layer limits their extraction efficiency and utilization effectiveness during photocatalysis.Herein,we fabricated a novel metalsemiconductor heterojunction(P2-Au)with ultrathin-shell semiconductor layer by combing ultra-small metal chalcogenide semiconductor clusters(P2)with gold nanorods(Au NRs),which exhibits high-efficiency extraction of hot electrons and photocatalytic application.The robust binding of P2 cluster,with its smaller volume and larger energy level splitting compared to large-sized quantum dots,not only significantly increases the yield of hot electrons but also enables their rapid extraction and sustains long-lived(>2 ns)high-energy states.As a proof of concept,the composite photocatalyst achieves near-infrared-lightdriven C(sp^(3))-S cross-coupling reactions for the first time.This protocol effectively produces over 50 alkylthioethers from a wide scope range of non-active alkyl bromides and chlorides,aryl and alkyl thiols.This work provides a new strategy for highefficiency extraction of hot electrons within plasmonic metal nanostructures and paves the way for hot electron-driven photocatalytic organic transformations.
基金This work was supported by the NSF of China(21822109,21805276,21773245,21773151,21975254)National Key R&D Program of China(2017YFA0206802)+2 种基金the Strategic Priority Research Program of Chinese Academy of Sciences(XDB20000000)Key Research Program of Frontier Science,Chinese Academy of Sciences(QYZDB-SSW-SLH023)Youth Innovation Promotion Association CAS,International Partnership Program of CAS(121835KYSB201800).
文摘Conductive coordination polymers(CCPs)have shown great potential for electronic purposes.However,their applications in photodetection have been limited by poor sensitivity,low on/off current ratio,and slow response owing to the low charge generation and/or separation efficiency.In this work,metal-to-ligand chargetransfer(MLCT)in PhSeAg was used to fabricate a single-component MLCT photodetecting material for the first time to solve the above challenges.The material obtained possesses ultrahigh sensitivity to weak-light intensity(0.03 mW cm^(−2)),the highest on/off ratio,and the fastest response speed than other wellknown CCPs materials tested.Our work might provide a simple but common strategy for designing high-performance CCPs composites for optoelectrical applications.
