A facile method for decarboxylative amination driven by the photoactivity of electron donor-acceptor(EDA)com-plexes assembled from iodide salts and redox-active esters has been proposed.A broad array of acyclic and cy...A facile method for decarboxylative amination driven by the photoactivity of electron donor-acceptor(EDA)com-plexes assembled from iodide salts and redox-active esters has been proposed.A broad array of acyclic and cyclic protected amines were readily synthesized without requiring exogenous transition-metal or photoredox catalysts.Moreover,this ap-proach facilitates late-stage functionalization of complex molecules and is amenable to continuous-flow process on gram scale.展开更多
Fluorescence-based imaging applications have been benefiting greatly from donor-acceptor(D-A)/donor-π-acceptor(D-π-A)fluorescent probes owing to their intramolecular charge transfer(ICT)nature and self-assembly beha...Fluorescence-based imaging applications have been benefiting greatly from donor-acceptor(D-A)/donor-π-acceptor(D-π-A)fluorescent probes owing to their intramolecular charge transfer(ICT)nature and self-assembly behavior.In this study,we design and synthesize a hydrophilic D-A fluorescent probe,namely CHBA,which would self-assemble into interlaced textures down to nanoscale but disassemble by trace amount of water in fingertip area.Upon finger-pressing,it enables fingerprint imaging and covers level-1/2/3 fingerprint information,wherein the sweat pores can be mapped in both bright field model and fluorescence mode,capable of naked-eye-based similarity analysis for personal identity verification(PIV).Spectroscopic analysis and morphology study show that the working mechanism can be attributed to the selective water-erosion effect on the solid-liquid interphase under physical contact.The sweat pore information can be digitized by polar coordinate conversion,further allowing machine-learning-based analysis for PIV application.The final PIV accuracy reaches 100%for all the involved machine-learning models,with no erroneous judgements.A prototype of PIV system is constructed by integrating CHBA with artificial intelligence hardware,wherein the sweat pore imaging,data processing and the decisionmaking could be run in parallel,suggesting high feasibility in real-world application.展开更多
Herein,we report the design and synthesis of alternating donor-acceptor nanorings[3]C-NA and[4]C-NA,along with a reference linear molecule[3]L-NA,via electrochemical oxidation-induced reductive elimination of alkynyl ...Herein,we report the design and synthesis of alternating donor-acceptor nanorings[3]C-NA and[4]C-NA,along with a reference linear molecule[3]L-NA,via electrochemical oxidation-induced reductive elimination of alkynyl platinum(II)complexes.Unlike[3]L-NA,which exhibits charge defects at its end-groups,the cyclic structures of[3]C-NA and[4]C-NA facilitate enhanced electron delocalization,enabling efficient charge transfer in low-polarity toluene.In the polar solvent dichloromethane(DCM),the increased flexibility of[4]C-NA promotes intramolecular charge transfer and suppresses charge recombination.The observed faster intramolecular charge transfer and slower charge recombination rates in these nanoring acceptor materials suggest their potential for improving the power conversion efficiency of organic solar cells,providing valuable insights for the design of nanoring acceptor materials.展开更多
The transition metal-free chalcogen trifluoromethylation of alkenes represents a highly efficient transformation for the rapid generation of C(sp3)-rich aliphatic trifluoromethyl compounds. However, a unified methodol...The transition metal-free chalcogen trifluoromethylation of alkenes represents a highly efficient transformation for the rapid generation of C(sp3)-rich aliphatic trifluoromethyl compounds. However, a unified methodology to achieve oxy-, thio-, and seleno-trifluoromethylation remains elusive yet highly desirable. In this study, we report a triarylamine-catalyzed three-component vicinal chalcogen-trifluoromethylation of alkenes under blue light irradiation without the need of transition metal catalyst. This reaction is broadly applicable to oxy, thio, and seleno nucleophiles, facilitating modular access to a diverse array of β-trifluoromethyl alcohols, ethers, thioethers, thiocyanates, and selenocyanates with good yields and predictable regioselectivities (61 examples). Additionally, we demonstrate its application in the late-stage modification of natural products and pharmaceutical compounds. Preliminary mechanistic studies suggest that a catalytic electron donor-acceptor (EDA) complex between triarylamine and the Umemoto reagent is key to enabling the radical/polar crossover process.展开更多
Aqueous zinc-ion batteries(AZIBs)have hugely latent advantages in large-scale energy storage due to its innate safety,reasonable price,and sustainability.However,most AZIB cathode materials suffer from short cycling l...Aqueous zinc-ion batteries(AZIBs)have hugely latent advantages in large-scale energy storage due to its innate safety,reasonable price,and sustainability.However,most AZIB cathode materials suffer from short cycling life and poor rate performance.Herein,a bipolar donor-acceptor(D-A)conjugated microporous polymer(PTZ-BDTB),consisting of electron-withdrawing benzo[1,2-b:4,5-b']dithiophene-4,8-dio ne(BDTB)units and electron-donating phenothiazine(PTZ)units,is developed as the cathode material of aqueous zinc dual-ion batteries(AZDIBs).The D-A type structure design could reduce the band gap,thus promoting electron transfer in the polymer framework.Therefore,the PTZ-BDTB cathode in a30 mol/kg(m)ZnCl_(2)water-in-salt electrolyte exhibits a high reversible capacity of 202 mA h g^(-1)at0.05 A g^(-1)with excellent rate performance(109 mA h g^(-1)at 15 A g^(-1)),which is far superior to its counterpart polymers PPTZ and PB-BDTB.Impressively,PTZ-BDTB shows ultra-stable cycle performance with capacity retention ratios of 76.2%after 460 cycles at 0.05 A g^(-1)and 96%after 27000 cycles at 5 A g^(-1).PTZBDTB also exhibits a low self-discharge ability with capacity retention about 76.4%after resting the battery for 28 days.These results demonstrate that D-A type structural design is a promising strategy for constructing high performance cathode materials for AZDIBs.展开更多
The development of donor-acceptor(D-A) conjugated polymers greatly promotes the device performance in organic electronics. Recently, the strategy of embedding pyridine units into D-A conjugated polymer backbones has a...The development of donor-acceptor(D-A) conjugated polymers greatly promotes the device performance in organic electronics. Recently, the strategy of embedding pyridine units into D-A conjugated polymer backbones has attracted much attention due to the resulted lowered LUMO levels. In addition, the possible non-bonding interactions resulted from the nitrogen atoms also improve the coplanarity of the polymer backbones. All these factors have great contribution to enhance the device performance. In this review, we summarized the recent development of pyridine-embedded D-A conjugated polymers and their applications in organic field-effect transistors(OFETs).展开更多
Self-assembled molecules(SAMs) have shown great potential in replacing bulk charge selective contact layers in high-performance perovskite solar cells(PSCs) due to their low material consumption and simple processing....Self-assembled molecules(SAMs) have shown great potential in replacing bulk charge selective contact layers in high-performance perovskite solar cells(PSCs) due to their low material consumption and simple processing. Herein, we design and synthesize a series of donor-acceptor(D-A) type SAMs(MPA-BTCA, MPA-BT-BA, and MPA-BT-RA, where MPA is 4-methoxy-N-(4-methoxyphenyl)-N-phenylaniline;BT is benzo[c][1,2,5]-thiadiazole;CA is 2-cyanoacrylic acid, BA is benzoic acid, RA is rhodanine-3-propionic acid) with distinct anchoring groups, which show dramatically different properties. MPA-BTCA with CA anchoring groups exhibited stronger dipole moments and formed a homogeneous monolayer on the indium tin oxide(ITO) surface by adopting an upstanding self-assembling mode. However, the MPA-BT-RA molecules tend to aggregate severely in solid state due to the sp~3 hybridization of the carbon atom on the RA group, which is not favorable for achieving a long-range ordered self-assembled layer.Consequently, benefiting from high dipole moment, as well as dense and uniform self-assembled film,the device based on MPA-BT-CA yielded a remarkable power conversion efficiency(PCE) of 21.81%.Encouragingly, an impressive PCE approaching 20% can still be obtained for the MPA-BT-CA-based PSCs as the device area is increased to 0.80 cm^(2). Our work sheds light on the design principles for developing hole selecting SAMs, which will pave a way for realizing highly efficient, flexible, and large-area PSCs.展开更多
The recent progress in the design and synthesis of high-performance donor-acceptor conjugated polymeric semiconducting materials is reviewed from the perspective of multiscale structures.The multiscale of conjugated p...The recent progress in the design and synthesis of high-performance donor-acceptor conjugated polymeric semiconducting materials is reviewed from the perspective of multiscale structures.The multiscale of conjugated polymers is from the primary one-dimensional polymer molecular scale to the secondary polymer-chains interaction scale,and then to the tertiary polymer aggregate scale.This review focuses on the design and synthesis of polymer molecules,proposes new classification rules,and rationally summarizes the design strategies and modulation methods of polymers.We describe the recent progress from these three aspects:(1)the modification ofπ-conjugated backbone,(2)the evolution of the polymerization methods,and(3)the regulation of aggregate-state structure.展开更多
Two acceptor-donor-acceptor(A-D-A)type non-fullerene acceptors(namely WH1 and WH7)containing the oxindole-based bridge are designed and synthesized for polymer solar cells(PSCs)applications.The bridge unit is introduc...Two acceptor-donor-acceptor(A-D-A)type non-fullerene acceptors(namely WH1 and WH7)containing the oxindole-based bridge are designed and synthesized for polymer solar cells(PSCs)applications.The bridge unit is introduced through a precursor(6-bromo-1-octylindoline-2,3-dione)that contains both bromine and carbonyl and provides the feasibility of the Pd-catalyzed cross-coupling reaction and the Knoevenagel condensation,respectively.This facile synthetic approach exhibits the potential to gain high performance non-fullerene acceptors through extendingπ-conjugated backbone with strong light-absorbing building blocks.The synthesis and properties of WH1 and WH7 are demonstrated with different endcap units,then PSCs are fabricated using PBDB-T:WH1 and PBDB-T:WH7 as the active layers,and attain an average power conversion efficiency(PCE)of 2.58%and 6.24%,respectively.Further device physics studies afford the deep insight of structure variation influence on the device performance.This work provides a facile non-fullerene acceptor design strategy and shows how structure variations impact the PSC performance.展开更多
A supramolecular bottlebrush polymer has been constructed in water through the self-assembly of a rigid electron-deficient building block and an electron-rich monomer which bears two tetraethylene glycol chains,driven...A supramolecular bottlebrush polymer has been constructed in water through the self-assembly of a rigid electron-deficient building block and an electron-rich monomer which bears two tetraethylene glycol chains,driven by CB[8]-encapsulation-enhanced donor-acceptor interaction.The as-formed supramolecular bottlebrush polymer has been characterized by -1H NMR titration experiment,UV-vis spectroscopy,DLS and 2D -1H NMR DOSY.展开更多
Organic solid-state luminescent materials with high-efficiency deep-red emission have attracted considerable interest in recent years.Constructing donor-acceptor(D-A)type molecules has been one of most commonly used s...Organic solid-state luminescent materials with high-efficiency deep-red emission have attracted considerable interest in recent years.Constructing donor-acceptor(D-A)type molecules has been one of most commonly used strategies to achieve deep-red emission,but it is always difficult to achieve high photoluminescence(PL)quantum yield(ηPL)due to forbidden charge-transfer state.Herein,we report a new D-A type molecule 4-(7-(4-(diphenylamino)phenyl)-9-oxo-9H-fluoren-2-yl)benzonitrile(TPAFOCN),deriving from donor-acceptor-donor(D-A-D)type 2,7-bis(4-(diphenylamino)phenyl)-9H-fluoren-9-one(DTPA-FO)with a fluorescence maximum of 627 nm in solids.This molecular design enables a transformation of acceptor from fluorenone(FO)itself to 4-(9-oxo-9H-fluoren-2-yl)benzonitrile(FOCN).Compared with DTPA-FO,the introduction of cyanophenyl not only shifts the emission of TPA-FOCN to deep red with a fluorescence maximum of 668 nm in solids,but also maintains the highηPL of 10%.Additionally,a solution-processed non-doped organic light-emitting diode(OLED)was fabricated with TPA-FOCN as emitter.TPA-FOCN device showed a maximum luminous efficiency of 0.13 cd/A and a maximum external quantum efficiency(EQE)of 0.22%with CIE coordinates of(0.64,0.35).This work provides a valuable strategy for the rational design of high-efficiency deep-red emission materials using cyanophenyl as an ancillary acceptor.展开更多
Based on graphene, a new class of second-order nonlinear optical（NLO） material, the lithium salt of NH2-substituted graphene nanoribbon with the twofold donor（D）/acceptor（A） mode, was reported. Eight stable 2Li-...Based on graphene, a new class of second-order nonlinear optical（NLO） material, the lithium salt of NH2-substituted graphene nanoribbon with the twofold donor（D）/acceptor（A） mode, was reported. Eight stable 2Li-2NH2-GNR lithium salts, especially cis lithium salts, display considerably large β0 values. The combination of NH2-substituting and cis Li-doping makes β0 greatly increased from 0（GNR） to 1.2×105―2.9×105 a.u.（cis-2Li- 2NH2-GNRs）. Our largest β0 value（2.9×105 a.u.） for cis-2Li-1,3-2NH2-AGNR is comparable to the record value of 1.7×105 a.u. for a long donor-acceptor polyene.展开更多
The design and synthesis of photoactive macrocyclic molecules continue to attract attention because such species play important roles in supramolecular chemistry as well as photoelectronic applications.Donoracceptor(D...The design and synthesis of photoactive macrocyclic molecules continue to attract attention because such species play important roles in supramolecular chemistry as well as photoelectronic applications.Donoracceptor(D-A)conjugated macrocycles are an emerging class of photoactive molecules due to their D-A conjugated structural characteristics and tunable optical properties.In addition,the well-defined cavities in such D-A macrocycles endow them with versatile host-vip properties.In this review,we provide a comprehensive summary of D-A conjugated macrocycle chemistry,detailing recent progress in the area of synthetic methods,optical properties,host-vip chemistry and applications of the underlying chemistry to chemical sensors,bioimaging and photoelectronic devices.Our objective is to provide not only a review of the fundamental findings,but also to outline future research directions where D-A conjugated macrocycles and their constructs may have a role to play.展开更多
The doping process and thermoelectric properties of donor-acceptor(D-A)type copolymers are investigated with the representative poly([2,6-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b]dithiophene]3-fluoro-2-[(2-ethylhe...The doping process and thermoelectric properties of donor-acceptor(D-A)type copolymers are investigated with the representative poly([2,6-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b]dithiophene]3-fluoro-2-[(2-ethylhexyl)-carbonyl]thieno[3,4-b]thiophenediyl))(PTB7-Th).The PTB7-Th is doped by Fe Cl;and only polarons are induced in its doped films.The results reveal that the electron-rich donor units within PTB7-Th lose electrons preferentially at the initial stage of the oxidation and then the acceptor units begin to be oxidized at a high doping concentration.The energy levels of polarons and the Fermi level of the doped PTB7-Th remain almost unchange with different doping levels.However,the morphology of the PTB7-Th films could be deteriorated as the doping levels are improved,which is one of the main reasons for the decrease of electrical conductivity at the later stage of doping.The best electrical conductivity and power factor are obtained to be 42.3 S·cm^(-1);and 33.9μW·mK^(-1),respectively,in the doped PTB7-Th film at room temperature.The power factor is further improved to 38.3μW·mK^(-1);at 75℃.This work may provide meaningful experience for development of D-A type thermoelectric copolymers and may further improve the doping efficiency.展开更多
The ground and excited state properties of the [60]fullerene, diphenylbenzothiadiazole-triphenylamine （PBTDP-TPA） dyad and fullerene-diphenylbenzothiadiazole-triphenylamine （fullerene-PBTDP-TPA） triad were investi...The ground and excited state properties of the [60]fullerene, diphenylbenzothiadiazole-triphenylamine （PBTDP-TPA） dyad and fullerene-diphenylbenzothiadiazole-triphenylamine （fullerene-PBTDP-TPA） triad were investigated theoretically using density functional theory with B3LYP functional and 3-21G basis set and time-dependent density functional theory with B3LYP functional and STO-3G basis set as well as 2D and 3D real space analysis methods. The 2D site representation reveals the electron-hole coherence on excitation. The 3D transition density shows the orientation and strength of the transition dipole moment, and the 3D charge difference density gives the orientation and result of the intramolecular charge transfer. Also photoinduced intermolecular charge transfer （ICT） in PBTDP-TPA-fullerene triad are identified with 2D and 3D representations, which reveals the mechanisms of ICT in donor-bridge-acceptor triad on excitation. Besides that we also found that the direct superexchange ICT from donor to acceptor （tunneling through the bridge） strongly promotes the ICT in the donor-bridge-acceptor triad.展开更多
Covalent organic frameworks(COFs)have attracted attention as photocatalysts,however,low electron transfer and reactive oxygen species(ROS)generation still hinder their photocatalytic application.In this work,we constr...Covalent organic frameworks(COFs)have attracted attention as photocatalysts,however,low electron transfer and reactive oxygen species(ROS)generation still hinder their photocatalytic application.In this work,we construct multivariate donor-acceptor(D-A)heterojunctions in the covalent organic frameworks by synchronously introducing electron-withdrawing and donating substituents.Importantly,the optoelectronic characteristics and visible-light photocatalytic performance were improved with the increase of the electron donor carbon chains in multivariate D-A COFs.Combining in‐situ characterization with theoretical calculations,the charge carrier separation and transfer efficiency,•O_(2)–generation and conversion,and the energy barrier of the rate determination steps related to the formation of*OH and*OOH,can be well regulated by the multivariate D-A COFs.More importantly,the ortho-carbon atom of the Br and OCH_(3) group-linked benzene rings and the imine bond(–C=N–)in COF-Br@OCH_(3) were activated to produce the key*OH and*OOH intermediates for effectively reducing the energy barrier of H2O oxidation and O_(2) reduction.This work provides valuable insights into the precise design and synthesis of COFs-based catalysts and the regulation of electron transfer and ROS generation by modulating the electron-withdrawing and donating substituents for highly efficient visible-light photocatalytic degradation of refractory organic pollutants.展开更多
Donor-acceptor （D-A） type fully conjugated block copolymer systems have been rarely reported due to the challenges in synthetic approaches to prepare well-defined low-polydispersity products. In this work, fully con...Donor-acceptor （D-A） type fully conjugated block copolymer systems have been rarely reported due to the challenges in synthetic approaches to prepare well-defined low-polydispersity products. In this work, fully conjugated block copolymers are synthesized in a one-pot reaction through Stille coupling polycondensation, by utilizing the end-functional polymer copolymerization method. End-functional P3HT are copolymerized with AA （2,7-dihromo-9-（heptadecan-9-yl）-9H- carbazole） and BB （4,7-bis（5-（trimethylstannyl）thiophen-2-yl）benzo[c][1,2,5]thiadiazole, TBT） type monomers, respectively. The orthogonal solubility between the very soluble P3HT donor and the insoluble PCDTBT acceptor block improves the purity of block copolymers as well as distinct nano-scale phase-separation compared with other reports on miscibility of donor and acceptor polymer block. Further purification via preparative GPC is carried out to remove the excess of unreacted P3HT and free PCDTBT as well as to achieve low polydispersity of block copolymers. The chemical structure of the P3HT- b-PCDTBT block copolymers are verified via IH-NMR, and further confirmed by FTIR spectra. The block copolymer shows broad absorption and moderate optical band gap of 1.8 eV. Furthermore, the fully conjugated block copolymer films exhibit significant fine structures, much smoother film morphology compared to P3HT/PCDTBT polymer blends. By adding a small amount of block copolymer P3HT-b-PCDTBT as a compatibilizer into the bulk-heterojunction of P3HT：PC61BM blends, polymer solar ceils with an 8% increase of short circuit current （Jse） and 10% increase of power conversion efficiency （PCE） are achieved owing to the improvement of the active-layer film morphology. To the best of our knowledge, this is the first report on donor-acceptor type fully conjugated block copolymer as an effective ternary additive in polymer： fullerene bulk heterojunction solar cells.展开更多
Novel donor-acceptor-donor structured small molecular hole transporting materials are developed through a facile route by crosslinking dithienopyrrolobenzothiadiazole and phenothiazine or triarylamine-based donor unit...Novel donor-acceptor-donor structured small molecular hole transporting materials are developed through a facile route by crosslinking dithienopyrrolobenzothiadiazole and phenothiazine or triarylamine-based donor units. The strong push/pull electron capability of dithienopyrrolobenzothiadiazole/ phenothiazine and large π-conjugated dithienopyrrolobenzothiadiazole facilitate hole mobility and high conductivity. The devices using the dithienopyrrolobenzothiadiazole/phenothiazine-based hole trans-porting material achieved a power conversion efficiency of 14.2% under 1 sun illumination and improved stability under 20% relative humidity at room temperature without encapsulation. The present finding highlights the potential of dithienopyrrolobenzothiadiazole-based donor-acceptor-donor small molecular hole transporting materials for perovskite solar cells.展开更多
Reduced rate constants of photoinduced electron transfer in intramolecular fluorescence quenching of donor-acceptor podands induced by cation-complexation are observed in the highly exothermic reactions.
An ortho-selective intermolecular photocycloaddition of commercially available quinolines has been developed using a strainrelease approach.This approach enabled the direct synthesis of quinoline-derived-semisaturated...An ortho-selective intermolecular photocycloaddition of commercially available quinolines has been developed using a strainrelease approach.This approach enabled the direct synthesis of quinoline-derived-semisaturated-fused rings in conjunction with cycloproarylketones as coupling partners.Mechanistic investigations have revealed that the generation of an electron donor acceptor complex between cycloproarylketones and camphorsulfonic acid,followed by radical addition with quinolines through a single electron transfer process,along with the excitation of the following adducts via energy transfer,is crucial for the observed photocycloaddition.展开更多
文摘A facile method for decarboxylative amination driven by the photoactivity of electron donor-acceptor(EDA)com-plexes assembled from iodide salts and redox-active esters has been proposed.A broad array of acyclic and cyclic protected amines were readily synthesized without requiring exogenous transition-metal or photoredox catalysts.Moreover,this ap-proach facilitates late-stage functionalization of complex molecules and is amenable to continuous-flow process on gram scale.
基金the financial support from National Natural Science Foundation of China(No.51703135)the technical support from Beijing Key Laboratory of Optical Materials and Photonic Devices。
文摘Fluorescence-based imaging applications have been benefiting greatly from donor-acceptor(D-A)/donor-π-acceptor(D-π-A)fluorescent probes owing to their intramolecular charge transfer(ICT)nature and self-assembly behavior.In this study,we design and synthesize a hydrophilic D-A fluorescent probe,namely CHBA,which would self-assemble into interlaced textures down to nanoscale but disassemble by trace amount of water in fingertip area.Upon finger-pressing,it enables fingerprint imaging and covers level-1/2/3 fingerprint information,wherein the sweat pores can be mapped in both bright field model and fluorescence mode,capable of naked-eye-based similarity analysis for personal identity verification(PIV).Spectroscopic analysis and morphology study show that the working mechanism can be attributed to the selective water-erosion effect on the solid-liquid interphase under physical contact.The sweat pore information can be digitized by polar coordinate conversion,further allowing machine-learning-based analysis for PIV application.The final PIV accuracy reaches 100%for all the involved machine-learning models,with no erroneous judgements.A prototype of PIV system is constructed by integrating CHBA with artificial intelligence hardware,wherein the sweat pore imaging,data processing and the decisionmaking could be run in parallel,suggesting high feasibility in real-world application.
基金support from Natural Science Foundation of China(Nos.22271239,22171237,22071208,and 92356308)the Natural Science Foundation of Fujian Province(2022J01524)。
文摘Herein,we report the design and synthesis of alternating donor-acceptor nanorings[3]C-NA and[4]C-NA,along with a reference linear molecule[3]L-NA,via electrochemical oxidation-induced reductive elimination of alkynyl platinum(II)complexes.Unlike[3]L-NA,which exhibits charge defects at its end-groups,the cyclic structures of[3]C-NA and[4]C-NA facilitate enhanced electron delocalization,enabling efficient charge transfer in low-polarity toluene.In the polar solvent dichloromethane(DCM),the increased flexibility of[4]C-NA promotes intramolecular charge transfer and suppresses charge recombination.The observed faster intramolecular charge transfer and slower charge recombination rates in these nanoring acceptor materials suggest their potential for improving the power conversion efficiency of organic solar cells,providing valuable insights for the design of nanoring acceptor materials.
基金the financial support provided by the National Natural Science Foundation of China(22361142832,92156025,22271212)the Science and Technology Project of Hebei Education Department Foundation(BJ2025192)We would like to thank Dr.Guosheng Ding,Dr.Kongying Zhu,and Dr.Xiaojuan Deng at the Analysis and Testing Center of Tianjin University for their assistance with NMR testing and analysis.
文摘The transition metal-free chalcogen trifluoromethylation of alkenes represents a highly efficient transformation for the rapid generation of C(sp3)-rich aliphatic trifluoromethyl compounds. However, a unified methodology to achieve oxy-, thio-, and seleno-trifluoromethylation remains elusive yet highly desirable. In this study, we report a triarylamine-catalyzed three-component vicinal chalcogen-trifluoromethylation of alkenes under blue light irradiation without the need of transition metal catalyst. This reaction is broadly applicable to oxy, thio, and seleno nucleophiles, facilitating modular access to a diverse array of β-trifluoromethyl alcohols, ethers, thioethers, thiocyanates, and selenocyanates with good yields and predictable regioselectivities (61 examples). Additionally, we demonstrate its application in the late-stage modification of natural products and pharmaceutical compounds. Preliminary mechanistic studies suggest that a catalytic electron donor-acceptor (EDA) complex between triarylamine and the Umemoto reagent is key to enabling the radical/polar crossover process.
基金financial supported by the National Natural Science Foundation of China(22175110&22375076,52103264)the Hubei Provincial Natural Science Foundation of China(2024AFA031)the Key Research and Development Program of Wuhan(2024010802030157)。
文摘Aqueous zinc-ion batteries(AZIBs)have hugely latent advantages in large-scale energy storage due to its innate safety,reasonable price,and sustainability.However,most AZIB cathode materials suffer from short cycling life and poor rate performance.Herein,a bipolar donor-acceptor(D-A)conjugated microporous polymer(PTZ-BDTB),consisting of electron-withdrawing benzo[1,2-b:4,5-b']dithiophene-4,8-dio ne(BDTB)units and electron-donating phenothiazine(PTZ)units,is developed as the cathode material of aqueous zinc dual-ion batteries(AZDIBs).The D-A type structure design could reduce the band gap,thus promoting electron transfer in the polymer framework.Therefore,the PTZ-BDTB cathode in a30 mol/kg(m)ZnCl_(2)water-in-salt electrolyte exhibits a high reversible capacity of 202 mA h g^(-1)at0.05 A g^(-1)with excellent rate performance(109 mA h g^(-1)at 15 A g^(-1)),which is far superior to its counterpart polymers PPTZ and PB-BDTB.Impressively,PTZ-BDTB shows ultra-stable cycle performance with capacity retention ratios of 76.2%after 460 cycles at 0.05 A g^(-1)and 96%after 27000 cycles at 5 A g^(-1).PTZBDTB also exhibits a low self-discharge ability with capacity retention about 76.4%after resting the battery for 28 days.These results demonstrate that D-A type structural design is a promising strategy for constructing high performance cathode materials for AZDIBs.
基金supported by National Key R&D Program of China (No. 2017YFA0204701)National Natural Science Foundation of China (Nos. 21722201, 21790360, 21420102005)the Major State Basic Research Development Program (No. 2015CB856505) from the MOST
文摘The development of donor-acceptor(D-A) conjugated polymers greatly promotes the device performance in organic electronics. Recently, the strategy of embedding pyridine units into D-A conjugated polymer backbones has attracted much attention due to the resulted lowered LUMO levels. In addition, the possible non-bonding interactions resulted from the nitrogen atoms also improve the coplanarity of the polymer backbones. All these factors have great contribution to enhance the device performance. In this review, we summarized the recent development of pyridine-embedded D-A conjugated polymers and their applications in organic field-effect transistors(OFETs).
基金financial support from the National Natural Science Foundation of China (NSFC)(21805128)the National Natural Science Foundation of China (21774055)+3 种基金the financial support from the National Natural Science Foundation of China(21975260)the Shenzhen Science and Technology Innovation Commission(JCYJ20180504165709042)financial support of Guangdong Provincial Key Laboratory Program(2021B1212040001) from the Department of Science and Technology of Guangdong Provincethe NSFC-CNR exchange program of NSFC(22011530391)。
文摘Self-assembled molecules(SAMs) have shown great potential in replacing bulk charge selective contact layers in high-performance perovskite solar cells(PSCs) due to their low material consumption and simple processing. Herein, we design and synthesize a series of donor-acceptor(D-A) type SAMs(MPA-BTCA, MPA-BT-BA, and MPA-BT-RA, where MPA is 4-methoxy-N-(4-methoxyphenyl)-N-phenylaniline;BT is benzo[c][1,2,5]-thiadiazole;CA is 2-cyanoacrylic acid, BA is benzoic acid, RA is rhodanine-3-propionic acid) with distinct anchoring groups, which show dramatically different properties. MPA-BTCA with CA anchoring groups exhibited stronger dipole moments and formed a homogeneous monolayer on the indium tin oxide(ITO) surface by adopting an upstanding self-assembling mode. However, the MPA-BT-RA molecules tend to aggregate severely in solid state due to the sp~3 hybridization of the carbon atom on the RA group, which is not favorable for achieving a long-range ordered self-assembled layer.Consequently, benefiting from high dipole moment, as well as dense and uniform self-assembled film,the device based on MPA-BT-CA yielded a remarkable power conversion efficiency(PCE) of 21.81%.Encouragingly, an impressive PCE approaching 20% can still be obtained for the MPA-BT-CA-based PSCs as the device area is increased to 0.80 cm^(2). Our work sheds light on the design principles for developing hole selecting SAMs, which will pave a way for realizing highly efficient, flexible, and large-area PSCs.
基金financially supported by the National Key R&D Program of‘Key Scientific Issues of Transformative Technology’(No.2018YFA0703200)the National Natural Science Foundation of China(Nos.U22A6002,91833306,21922511 and 51873216)+4 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB30000000)the CAS Project for Young Scientists in Basic Research(No.YSBR-053)the CAS-Croucher Funding Scheme for Joint Laboratoriesthe CAS Cooperation Project(No.121111KYSB20200036)the Lu Jiaxi international team(No.GJTD-2020-02)。
文摘The recent progress in the design and synthesis of high-performance donor-acceptor conjugated polymeric semiconducting materials is reviewed from the perspective of multiscale structures.The multiscale of conjugated polymers is from the primary one-dimensional polymer molecular scale to the secondary polymer-chains interaction scale,and then to the tertiary polymer aggregate scale.This review focuses on the design and synthesis of polymer molecules,proposes new classification rules,and rationally summarizes the design strategies and modulation methods of polymers.We describe the recent progress from these three aspects:(1)the modification ofπ-conjugated backbone,(2)the evolution of the polymerization methods,and(3)the regulation of aggregate-state structure.
基金National Natural Science Foundation of China(No.21805032)Natural Science Foundation of Shanghai,China(No.19ZR1401400)Fundamental Research Funds for the Central Universities,China(No.20D128502).
文摘Two acceptor-donor-acceptor(A-D-A)type non-fullerene acceptors(namely WH1 and WH7)containing the oxindole-based bridge are designed and synthesized for polymer solar cells(PSCs)applications.The bridge unit is introduced through a precursor(6-bromo-1-octylindoline-2,3-dione)that contains both bromine and carbonyl and provides the feasibility of the Pd-catalyzed cross-coupling reaction and the Knoevenagel condensation,respectively.This facile synthetic approach exhibits the potential to gain high performance non-fullerene acceptors through extendingπ-conjugated backbone with strong light-absorbing building blocks.The synthesis and properties of WH1 and WH7 are demonstrated with different endcap units,then PSCs are fabricated using PBDB-T:WH1 and PBDB-T:WH7 as the active layers,and attain an average power conversion efficiency(PCE)of 2.58%and 6.24%,respectively.Further device physics studies afford the deep insight of structure variation influence on the device performance.This work provides a facile non-fullerene acceptor design strategy and shows how structure variations impact the PSC performance.
基金the National Natural Science Foundation of China(No.21402228)for financial support
文摘A supramolecular bottlebrush polymer has been constructed in water through the self-assembly of a rigid electron-deficient building block and an electron-rich monomer which bears two tetraethylene glycol chains,driven by CB[8]-encapsulation-enhanced donor-acceptor interaction.The as-formed supramolecular bottlebrush polymer has been characterized by -1H NMR titration experiment,UV-vis spectroscopy,DLS and 2D -1H NMR DOSY.
基金supported by the National Natural Science Foundation of China(Nos.91833304,51873077,51803071 and51673083)the National Basic Research Program of China(Nos.2015CB655003 and 2016YFB0401001)+2 种基金the Postdoctoral Innovation Talent Support Project(Nos.BX201700097 and BX20180121)the China Postdoctoral Science Foundation(Nos.2017M620108 and2018M641767)JLUSTIRT(No.2019TD-33)
文摘Organic solid-state luminescent materials with high-efficiency deep-red emission have attracted considerable interest in recent years.Constructing donor-acceptor(D-A)type molecules has been one of most commonly used strategies to achieve deep-red emission,but it is always difficult to achieve high photoluminescence(PL)quantum yield(ηPL)due to forbidden charge-transfer state.Herein,we report a new D-A type molecule 4-(7-(4-(diphenylamino)phenyl)-9-oxo-9H-fluoren-2-yl)benzonitrile(TPAFOCN),deriving from donor-acceptor-donor(D-A-D)type 2,7-bis(4-(diphenylamino)phenyl)-9H-fluoren-9-one(DTPA-FO)with a fluorescence maximum of 627 nm in solids.This molecular design enables a transformation of acceptor from fluorenone(FO)itself to 4-(9-oxo-9H-fluoren-2-yl)benzonitrile(FOCN).Compared with DTPA-FO,the introduction of cyanophenyl not only shifts the emission of TPA-FOCN to deep red with a fluorescence maximum of 668 nm in solids,but also maintains the highηPL of 10%.Additionally,a solution-processed non-doped organic light-emitting diode(OLED)was fabricated with TPA-FOCN as emitter.TPA-FOCN device showed a maximum luminous efficiency of 0.13 cd/A and a maximum external quantum efficiency(EQE)of 0.22%with CIE coordinates of(0.64,0.35).This work provides a valuable strategy for the rational design of high-efficiency deep-red emission materials using cyanophenyl as an ancillary acceptor.
基金Supported by the National Natural Science Foundation of China(Nos.20773046, 20773048 and 21073075)
文摘Based on graphene, a new class of second-order nonlinear optical（NLO） material, the lithium salt of NH2-substituted graphene nanoribbon with the twofold donor（D）/acceptor（A） mode, was reported. Eight stable 2Li-2NH2-GNR lithium salts, especially cis lithium salts, display considerably large β0 values. The combination of NH2-substituting and cis Li-doping makes β0 greatly increased from 0（GNR） to 1.2×105―2.9×105 a.u.（cis-2Li- 2NH2-GNRs）. Our largest β0 value（2.9×105 a.u.） for cis-2Li-1,3-2NH2-AGNR is comparable to the record value of 1.7×105 a.u. for a long donor-acceptor polyene.
基金supported by the National Natural Science Foundation of China(Nos.21971041 and 22001039)Natural Science Foundation of Fujian Province(No.2020J01447).
文摘The design and synthesis of photoactive macrocyclic molecules continue to attract attention because such species play important roles in supramolecular chemistry as well as photoelectronic applications.Donoracceptor(D-A)conjugated macrocycles are an emerging class of photoactive molecules due to their D-A conjugated structural characteristics and tunable optical properties.In addition,the well-defined cavities in such D-A macrocycles endow them with versatile host-vip properties.In this review,we provide a comprehensive summary of D-A conjugated macrocycle chemistry,detailing recent progress in the area of synthetic methods,optical properties,host-vip chemistry and applications of the underlying chemistry to chemical sensors,bioimaging and photoelectronic devices.Our objective is to provide not only a review of the fundamental findings,but also to outline future research directions where D-A conjugated macrocycles and their constructs may have a role to play.
基金supported by the National Key Research and Development Program of China(Grant No.Q2019YFE0107200)。
文摘The doping process and thermoelectric properties of donor-acceptor(D-A)type copolymers are investigated with the representative poly([2,6-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b]dithiophene]3-fluoro-2-[(2-ethylhexyl)-carbonyl]thieno[3,4-b]thiophenediyl))(PTB7-Th).The PTB7-Th is doped by Fe Cl;and only polarons are induced in its doped films.The results reveal that the electron-rich donor units within PTB7-Th lose electrons preferentially at the initial stage of the oxidation and then the acceptor units begin to be oxidized at a high doping concentration.The energy levels of polarons and the Fermi level of the doped PTB7-Th remain almost unchange with different doping levels.However,the morphology of the PTB7-Th films could be deteriorated as the doping levels are improved,which is one of the main reasons for the decrease of electrical conductivity at the later stage of doping.The best electrical conductivity and power factor are obtained to be 42.3 S·cm^(-1);and 33.9μW·mK^(-1),respectively,in the doped PTB7-Th film at room temperature.The power factor is further improved to 38.3μW·mK^(-1);at 75℃.This work may provide meaningful experience for development of D-A type thermoelectric copolymers and may further improve the doping efficiency.
基金This work was supported by the National Natural Science Foundation of China （No.10374040, No.20703064, and No.10505001） and the Postdoctoral Science Foundation of China （No.20060390017）.
文摘The ground and excited state properties of the [60]fullerene, diphenylbenzothiadiazole-triphenylamine （PBTDP-TPA） dyad and fullerene-diphenylbenzothiadiazole-triphenylamine （fullerene-PBTDP-TPA） triad were investigated theoretically using density functional theory with B3LYP functional and 3-21G basis set and time-dependent density functional theory with B3LYP functional and STO-3G basis set as well as 2D and 3D real space analysis methods. The 2D site representation reveals the electron-hole coherence on excitation. The 3D transition density shows the orientation and strength of the transition dipole moment, and the 3D charge difference density gives the orientation and result of the intramolecular charge transfer. Also photoinduced intermolecular charge transfer （ICT） in PBTDP-TPA-fullerene triad are identified with 2D and 3D representations, which reveals the mechanisms of ICT in donor-bridge-acceptor triad on excitation. Besides that we also found that the direct superexchange ICT from donor to acceptor （tunneling through the bridge） strongly promotes the ICT in the donor-bridge-acceptor triad.
文摘Covalent organic frameworks(COFs)have attracted attention as photocatalysts,however,low electron transfer and reactive oxygen species(ROS)generation still hinder their photocatalytic application.In this work,we construct multivariate donor-acceptor(D-A)heterojunctions in the covalent organic frameworks by synchronously introducing electron-withdrawing and donating substituents.Importantly,the optoelectronic characteristics and visible-light photocatalytic performance were improved with the increase of the electron donor carbon chains in multivariate D-A COFs.Combining in‐situ characterization with theoretical calculations,the charge carrier separation and transfer efficiency,•O_(2)–generation and conversion,and the energy barrier of the rate determination steps related to the formation of*OH and*OOH,can be well regulated by the multivariate D-A COFs.More importantly,the ortho-carbon atom of the Br and OCH_(3) group-linked benzene rings and the imine bond(–C=N–)in COF-Br@OCH_(3) were activated to produce the key*OH and*OOH intermediates for effectively reducing the energy barrier of H2O oxidation and O_(2) reduction.This work provides valuable insights into the precise design and synthesis of COFs-based catalysts and the regulation of electron transfer and ROS generation by modulating the electron-withdrawing and donating substituents for highly efficient visible-light photocatalytic degradation of refractory organic pollutants.
基金financially supported by the National Natural Science Foundation of China(No.21304047)Natural Science Foundation of Jiangsu Province(No.13KJB430017)+1 种基金Research Fund for the Doctoral Program of Higher Education(No.20133221120015)Synergetic Innovation Center for Organic Electronics and Information Displays
文摘Donor-acceptor （D-A） type fully conjugated block copolymer systems have been rarely reported due to the challenges in synthetic approaches to prepare well-defined low-polydispersity products. In this work, fully conjugated block copolymers are synthesized in a one-pot reaction through Stille coupling polycondensation, by utilizing the end-functional polymer copolymerization method. End-functional P3HT are copolymerized with AA （2,7-dihromo-9-（heptadecan-9-yl）-9H- carbazole） and BB （4,7-bis（5-（trimethylstannyl）thiophen-2-yl）benzo[c][1,2,5]thiadiazole, TBT） type monomers, respectively. The orthogonal solubility between the very soluble P3HT donor and the insoluble PCDTBT acceptor block improves the purity of block copolymers as well as distinct nano-scale phase-separation compared with other reports on miscibility of donor and acceptor polymer block. Further purification via preparative GPC is carried out to remove the excess of unreacted P3HT and free PCDTBT as well as to achieve low polydispersity of block copolymers. The chemical structure of the P3HT- b-PCDTBT block copolymers are verified via IH-NMR, and further confirmed by FTIR spectra. The block copolymer shows broad absorption and moderate optical band gap of 1.8 eV. Furthermore, the fully conjugated block copolymer films exhibit significant fine structures, much smoother film morphology compared to P3HT/PCDTBT polymer blends. By adding a small amount of block copolymer P3HT-b-PCDTBT as a compatibilizer into the bulk-heterojunction of P3HT：PC61BM blends, polymer solar ceils with an 8% increase of short circuit current （Jse） and 10% increase of power conversion efficiency （PCE） are achieved owing to the improvement of the active-layer film morphology. To the best of our knowledge, this is the first report on donor-acceptor type fully conjugated block copolymer as an effective ternary additive in polymer： fullerene bulk heterojunction solar cells.
基金Financial support from the 973 Program of China(No.2014CB643506)the NSFC Major International(Regional)Joint Research Project NSFC-SNSF(51661135023)+2 种基金NSFC(21673091,21702147)the Fundamental Research Funds For the Central Universities HUST(2018KFYXKJC034)the Opening Project of Zhejiang Provincial Top Key Discipline of Pharmaceutical Sciences
文摘Novel donor-acceptor-donor structured small molecular hole transporting materials are developed through a facile route by crosslinking dithienopyrrolobenzothiadiazole and phenothiazine or triarylamine-based donor units. The strong push/pull electron capability of dithienopyrrolobenzothiadiazole/ phenothiazine and large π-conjugated dithienopyrrolobenzothiadiazole facilitate hole mobility and high conductivity. The devices using the dithienopyrrolobenzothiadiazole/phenothiazine-based hole trans-porting material achieved a power conversion efficiency of 14.2% under 1 sun illumination and improved stability under 20% relative humidity at room temperature without encapsulation. The present finding highlights the potential of dithienopyrrolobenzothiadiazole-based donor-acceptor-donor small molecular hole transporting materials for perovskite solar cells.
基金We are grateful to the National NatUral Science Foundation of China for support this work.!(grantNO. 29733100)
文摘Reduced rate constants of photoinduced electron transfer in intramolecular fluorescence quenching of donor-acceptor podands induced by cation-complexation are observed in the highly exothermic reactions.
基金supported by the National Natural Science Foundation of China(21925103,22271077,21901062)the Natural Science Foundation of Henan Province(222301420046,232300421078)+1 种基金the Program for Science&Technology Innovation Talents in Universities of Henan Province(24HASTIT001)the China Postdoctoral Science Foundation(2021M690890)。
文摘An ortho-selective intermolecular photocycloaddition of commercially available quinolines has been developed using a strainrelease approach.This approach enabled the direct synthesis of quinoline-derived-semisaturated-fused rings in conjunction with cycloproarylketones as coupling partners.Mechanistic investigations have revealed that the generation of an electron donor acceptor complex between cycloproarylketones and camphorsulfonic acid,followed by radical addition with quinolines through a single electron transfer process,along with the excitation of the following adducts via energy transfer,is crucial for the observed photocycloaddition.
