Tactile perception plays a vital role for the human body and is also highly desired for smart prosthesis and advanced robots.Compared to active sensing devices,passive piezoelectric and triboelectric tactile sensors c...Tactile perception plays a vital role for the human body and is also highly desired for smart prosthesis and advanced robots.Compared to active sensing devices,passive piezoelectric and triboelectric tactile sensors consume less power,but lack the capability to resolve static stimuli.Here,we address this issue by utilizing the unique polarization chemistry of conjugated polymers for the first time and propose a new type of bioinspired,passive,and bio-friendly tactile sensors for resolving both static and dynamic stimuli.Specifically,to emulate the polarization process of natural sensory cells,conjugated polymers(including poly(3,4-ethylenedioxythiophen e):poly(styrenesulfonate),polyaniline,or polypyrrole)are controllably polarized into two opposite states to create artificial potential differences.The controllable and reversible polarization process of the conjugated polymers is fully in situ characterized.Then,a micro-structured ionic electrolyte is employed to imitate the natural ion channels and to encode external touch stimulations into the variation in potential difference outputs.Compared with the currently existing tactile sensing devices,the developed tactile sensors feature distinct characteristics including fully organic composition,high sensitivity(up to 773 mV N^(−1)),ultralow power consumption(nW),as well as superior bio-friendliness.As demonstrations,both single point tactile perception(surface texture perception and material property perception)and two-dimensional tactile recognitions(shape or profile perception)with high accuracy are successfully realized using self-defined machine learning algorithms.This tactile sensing concept innovation based on the polarization chemistry of conjugated polymers opens up a new path to create robotic tactile sensors and prosthetic electronic skins.展开更多
In conjugated polymers(CPs)photocatalytic system,the generation of reactive oxygen species(ROS)is regulated by cross-scale factors involving active site,excitonic behavior,and O_(2)activation process on the surface.Ho...In conjugated polymers(CPs)photocatalytic system,the generation of reactive oxygen species(ROS)is regulated by cross-scale factors involving active site,excitonic behavior,and O_(2)activation process on the surface.However,research on exploring the domino effect of“structure→excitonic behavior→O_(2)activation→photocatalytic reaction”through structural modification at the atomic scale remains at its early stages.Herein,two heptazine-based CPs,CP-DPA,and CP-CZ were successfully prepared by polymerization of precursors formed by reacting diphenylamine(DPA)and carbazole(CZ)with cyameluric chloride,respectively.The minute difference in single bond between DPA and CZ endows the polymers with distinct physicochemical properties.Owing to the rotation between benzene rings,CP-DPA exhibits relatively lower conjugation,resulting in increased exciton binding energy(Eb)and inhibited exciton dissociation.Meanwhile,its more triplet state excitons facilitate energy transfer to generate singlet oxygen.Therefore,CP-DPA shows excellent activity for phenylboronic acid oxidation.Conversely,CP-CZ possesses relatively higher conjugation,minimal Eb and intensified exciton dissociation,which promotes charge transfer to produce superoxide radical.Consequently,CP-CZ displays optimal activity for phe-nylacetylene oxidation and[3+2]cycloaddition.This work provides new insights into regulating ROS gener-ation by modulating the composition and structure of photocatalysts at the atomic scale.展开更多
Conjugated polymers(CPs)have emerged as an interesting class of materials in modern electronics and photonics,characterized by their unique delocalizedπ-electron systems that confer high flexibility,tunable electroni...Conjugated polymers(CPs)have emerged as an interesting class of materials in modern electronics and photonics,characterized by their unique delocalizedπ-electron systems that confer high flexibility,tunable electronic properties,and solution processability.These organic polymers present a compelling alternative to traditional inorganic semiconductors,offering the potential for a new generation of optoelectronic devices.This review explores the evolving role of CPs,exploring the molecular design strategies and innovative approaches that enhance their optoelectronic properties.We highlight notable progress toward developing faster,more efficient,and environmentally friendly devices by analyzing recent advancements in CP-based devices,including organic photovoltaics,field-effect transistors,and nonvolatile memories.The integration of CPs in flexible sustainable technologies underscores their potential to revolutionize future electronic and photonic systems.As ongoing research pushes the frontiers of molecular engineering and device architecture,CPs are poised to play an essential role in shaping next-generation technologies that prioritize performance,sustainability,and adaptability.展开更多
Solar-driven hydrogen peroxide(H_(2)O_(2))production offers a sustainable and environmentally friendly alternative to the traditional anthraquinone oxidation method.Conjugated polymers(CPs)are emerging as promising ph...Solar-driven hydrogen peroxide(H_(2)O_(2))production offers a sustainable and environmentally friendly alternative to the traditional anthraquinone oxidation method.Conjugated polymers(CPs)are emerging as promising photocatalysts for H_(2)O_(2)production due to their unique electronic,optical properties,and tunable structures.However,the high exciton binding energy of CPs hinders efficient exciton dissociation and charge separation,limiting their photocatalytic performance.In this work,we synthesized scandium(Sc)atoms decorated CPs with enhanced ordered stacking and crystallinity by introducing benzaldehyde as an end-capping reagent.The strong interaction between charged Sc atoms and electrons facilitates exciton dissociation and improves charge transfer capability.Furthermore,the Lewis acidic nature of Sc atoms promotes oxygen adsorption and enhances the stabilization of superoxide anion intermediate(·O_(2)^(-)).As a result,the as-synthesized photocatalysts exhibit a high H_(2)O_(2)production rate of 18μmol h^(-1)in pure water,which is three times that of pristine CPs,This work provides valuable insights into the design of organic polymer photocatalysts for various photocatalytic reactions.展开更多
In this work,the“functionalization-polymerization”(FP)method has been used to construct fullerene-contained double-cable conjugated polymers with“donor-acceptor”backbones.It was realized via synthesizing a fullere...In this work,the“functionalization-polymerization”(FP)method has been used to construct fullerene-contained double-cable conjugated polymers with“donor-acceptor”backbones.It was realized via synthesizing a fullerene-contained monomer and performing Stille polymerization.With this method,a series of double-cable conjugated polymers with different fullerene contents were developed and applied into single-component organic solar cells.The power conversion efficiencies(PCEs)based on these polymers increased from 0.71%to 1.71%with the enhanced fullerene contents.The relatively low PCEs might be originated from the poor microstructure in these polymers.These new conjugated polymers with molecular heterojunction would show potential application in organic electronic devices.展开更多
Exploring the charge transport properties and electronic functions of molecules is of primary interest in the area of molecular electronics.Conjugated polymers（CPs） represent an attractive class of molecular candida...Exploring the charge transport properties and electronic functions of molecules is of primary interest in the area of molecular electronics.Conjugated polymers（CPs） represent an attractive class of molecular candidates,benefiting from their outstanding optoelectronic properties.However,they have been less studied compared with the small-molecule family,mainly due to the difficulties in incorporating CPs into molecular junctions.In this review,we present a summary on how to fabricate CP-based singlechain and monolayered junctions,then discuss the transport behaviors of CPs in different junction architectures and finally introduce the potential applications of CPs in molecular-scale electronic devices.Although the research on CP-based molecular electronics is still at the initial stage,it is widely accepted that（1） CP chains are able to mediate long-range charge transport if their molecular electronic structures are properly designed,which makes them potential molecular wires,and（2） the intrinsic optoelectronic properties of CPs and the possibility of incorporating desirable functionalities by synthetic strategies imply the potential of employing tailor-made polymeric components as alternatives to small molecules for future molecular-scale electronics.展开更多
Development of organic semiconductors is one of the most intriguing and productive topics in material science and engineering. Many efforts have been made on the synthesis of aromatic building blocks such as benzene, ...Development of organic semiconductors is one of the most intriguing and productive topics in material science and engineering. Many efforts have been made on the synthesis of aromatic building blocks such as benzene, thiophene and pyrrole due to the facile preparation accompanied by the intrinsic environmental stability and relatively efficient properties of the resulting polymers. In the past, furan has been less explored in this field because of its high oxidation potential. Recently, furan has attracted obsession due to its weaker aromaticity, the greater solubilities of furan-containing π-conjugated polymers relative to other benzenoid systems and the accessibility of furan-based starting materials from renewable resources. This review elaborates the advancements of organic photovoltaic polymers containing furan building blocks. The uniqueness and advantages of furan-containing building blocks in semiconducting materials are also discussed.展开更多
Wearable biosensors have received great interest as patient-friendly diagnostic technologies because of their high flexibility and conformability.The growing research and utilization of novel materials in designing we...Wearable biosensors have received great interest as patient-friendly diagnostic technologies because of their high flexibility and conformability.The growing research and utilization of novel materials in designing wearable biosensors have accelerated the development of point-of-care sensing platforms and implantable biomedical devices in human health care.Among numerous potential materials,conjugated polymers(CPs)are emerging as ideal choices for constructing high-performance wearable biosensors because of their outstanding conductive and mechanical properties.Recently,CPs have been extensively incorporated into various wearable biosensors to monitor a range of target biomolecules.However,fabricating highly reliable CP-based wearable biosensors for practical applications remains a significant challenge,necessitating novel developmental strategies for enhancing the viability of such biosensors.Accordingly,this review aims to provide consolidated scientific evidence by summarizing and evaluating recent studies focused on designing and fabricating CP-based wearable biosensors,thereby facilitating future research.Emphasizing the superior properties and benefits of CPs,this review aims to clarify their potential applicability within this field.Furthermore,the fundamentals and main components of CP-based wearable biosensors and their sensing mechanisms are discussed in detail.The recent advancements in CP nanostructures and hybridizations for improved sensing performance,along with recent innovations in next-generation wearable biosensors are highlighted.CPbased wearable biosensors have been—and will continue to be—an ideal platform for developing effective and user-friendly diagnostic technologies for human health monitoring.展开更多
In principle,conjugated polymers can work as electron donors and thus as low-cost p-type organic semiconductors to transport holes in photovoltaic devices.With the booming interests in high-efficiency and low-cost sol...In principle,conjugated polymers can work as electron donors and thus as low-cost p-type organic semiconductors to transport holes in photovoltaic devices.With the booming interests in high-efficiency and low-cost solar cells to tackle global climate change and energy shortage,hole transporting materials(HTMs)based on conjugated polymers have received increasing attention in the past decade.In this perspective,recent advances in HTMs for a range of photovoltaic devices including dye-sensitized solar cells(DSSCs),perovskite solar cells(PSCs),and silicon(Si)/organic heterojunction solar cells(HSCs)are summarized and perspectives on their future development are also presented.展开更多
Four new low-band-gap alternating copolymers （P-1, P-2, P-3 and P-4） based on electron-rich benzodithiophene and newly developed electron-deficient units, thienopyrazine or dithiadiazatrindene derivatives, were synt...Four new low-band-gap alternating copolymers （P-1, P-2, P-3 and P-4） based on electron-rich benzodithiophene and newly developed electron-deficient units, thienopyrazine or dithiadiazatrindene derivatives, were synthesized by Stille polycondensation. All polymers exhibit good solubility in common organic solvents and a broad absorption band in the visible to near-infrared regions. The film optical band gaps of the polymers are in the range of 1.28-2.07 eV and the highest occupied molecular orbital （HOMO） energy levels are in the range of-4.99 eV to -5.28 eV. Bulk heterojunction polymer solar cells （PSCs） of the polymers were fabricated with phenyl-C61-butyric acid methyl ester （PC61BM） as acceptor material, and a power conversion efficiency of 0.80% was realized with P-1 as donor material.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
Herein, we reported a new label-free and fluorescence turn-on biosensor based on cationic conjugated poly（9,9-bis（6＇-N,N,N-trimethylammonium）hexyl）fluorine phenylene）（PFP） and perylene diimide derivatives（PDI...Herein, we reported a new label-free and fluorescence turn-on biosensor based on cationic conjugated poly（9,9-bis（6＇-N,N,N-trimethylammonium）hexyl）fluorine phenylene）（PFP） and perylene diimide derivatives（PDI）. Cationic PFP, single-stranded nucleic acid and PDI were used as signal reporter, probe and fluorescence quencher, respectively. In the presence of nucleic acids, they form complexes with PFP and PDI through strong electrostatic attraction interactions, resulting in PDI aggregating on nucleic acids and fluorescence of PFP being quenched. When nucleic acids are hydrolyzed by enzymes or their conformation is changed via recognizing targets, the effective aggregation of PDI is disrupted and the quenching ability is decreased. Thus the fluorescence of PFP recovers significantly. By taking advantage of the mechanism, we construct a new biosensor for endonuclease and small molecules detection. Here, S1 nuclease and bisphenol A are used as model systems. The detection limit of the SI nuclease and BPA are1.0×10^-6U/mL and 0.05 ng/mL, respectively. Our method is sensitive, cost-effective and simple, and provides a new platform for bioanalysis.展开更多
The development of donor-acceptor(D-A)type conjugated polymers depends largely on the design of novel A building blocks.Herein,we report a novel A building block based on the cyano-substituted organoboron unit(SBN-3)....The development of donor-acceptor(D-A)type conjugated polymers depends largely on the design of novel A building blocks.Herein,we report a novel A building block based on the cyano-substituted organoboron unit(SBN-3).Compared with the most common fluorine-substituted B←N unit,SBN-3 displays a significantly downshifted LUMO energy level because of the strong electron-withdrawing ability of cyano groups.In addition,due to the greater impact of cyano substitution on LUMO than on HOMO,SBN-3 exhibits a reduced band gap,nearinfrared absorption and fluorescence properties.The D-A type conjugated polymers based on the cyano-substituted B←N unit with thiophene-based units show narrow optical band gaps of ca.1.3 e V as well as distinctive electronic structures,i.e.,delocalized LUMOs and localized HOMOs.This work thus provides not only an effective approach to design strong A units but also a new electron-deficient building block for D-A type conjugated polymers.展开更多
Three novel conjugated polymers bearing 3,4-bis（4-hexylthiophen-2-yl）-3-cyclobutene-1,2-dione unit in their main chain have been synthesized successfully in good yields through Suzuki or Stille coupling reaction.The...Three novel conjugated polymers bearing 3,4-bis（4-hexylthiophen-2-yl）-3-cyclobutene-1,2-dione unit in their main chain have been synthesized successfully in good yields through Suzuki or Stille coupling reaction.Their molecular structures have been confirmed by FT-IR,~1H NMR and ^（13）C NMR.All these copolymers exhibit broad and strong absorption bands in UV-vis region,and their optical band gaps are calculated to be 1.6-2.0 eV.suggesting that they have good coverage with the solar spectrum.These polymers have good thermostability and solubility in common organic solvents.Moreover,all these objective macromolecules possess high electron affinity of～3.8 eV determined from cyclic voltammetry measurement,implying that they are potential n-type polymeric photovoltaic materials.展开更多
The development of n-type polymer thermoelectrics lags far behind that of p-type ones in view of material diversity and performance.New structural insights into the thermoelectric performance are needed for efficient ...The development of n-type polymer thermoelectrics lags far behind that of p-type ones in view of material diversity and performance.New structural insights into the thermoelectric performance are needed for efficient n-type polymer thermoelectric materials.Herein,we developed three acceptor-acceptor type organoboron polymers and investigated the effect of backbone configuration on thermoelectric performance.The three polymers are designed based on double B←N bridged bipyridine(BNBP)unit with monomeric thieno[3,4-c]pyrrole-4,6-dione(TPD),TPD dimer and TPD trimer as the copolymerizing units,respectively.The three polymers show similar low LUMO energy levels but different backbone configuration.Compared with the wavy backbone configuration,the pseudo-straight backbone configuration imparts the polymer with much enhanced crystallinity and electron mobility.As a result,after n-doping,the polymer with pseudo-straight configuration shows much higher electronic conductivity and power factor.We think these findings could serve as important guidelines for molecular design toward efficient n-type polymer thermoelectric materials.展开更多
The photovoltaic properties of double-cable conjugated polymers are significantly influenced by the length of the alkyl linkers that connect donor backbones and acceptor side units. In this study, a series of 2-(3-oxo...The photovoltaic properties of double-cable conjugated polymers are significantly influenced by the length of the alkyl linkers that connect donor backbones and acceptor side units. In this study, a series of 2-(3-oxo-2,3-dihydroinden-1-ylidene)malononitrile(IC)-based double-cable polymers with alkyl linkers ranging from C_8H_(16)to C_(16)H_(32)(Px, x = 8, 10, 12, 14, 16) were synthesized for single-component organic solar cells(SCOSCs). Among these, the linker length x = 12(P12) is found to optimize the power conversion efficiencies(PCEs) in SCOSCs. Specifically, PCEs increase from P8 to P12 and then decline from P12to P16. Detailed investigations of optical absorption, charge transport, and morphology provide insights into the underlying factors contributing to these PCE variations. The findings indicate that the exceptional photovoltaic properties observed in P12 can be attributed to three key factors: A delicate balance between enhanced charge separation facilitated by the increased spacer length and reduced crystallinity resulting from longer spacers, higher charge mobilities, and well-balanced hole/electron transport characteristics. This study highlights the critical role of linker length in determining the photovoltaic properties of double-cable conjugated polymer-based SCOSCs and offers valuable guidance for the design of novel double-cable conjugated polymers.展开更多
The absorption,scattering,and autofluorescence of biological tissues in short-wave infrared re-gion(SWIR,900-1700 nm)are relatively low,so SWIR fluorescence usually has deeper pene-tration into living tissues,and can ...The absorption,scattering,and autofluorescence of biological tissues in short-wave infrared re-gion(SWIR,900-1700 nm)are relatively low,so SWIR fluorescence usually has deeper pene-tration into living tissues,and can show a higher signal-to-noise ratio when used for imaging in vivo.However,there are few types of organic SWIR fluorescent materials currently.In this work,p-azaquinodimethane(p-AQM)with a quinoid structure is used as the acceptor unit,and car-bazole or fluorene with sp3 hybridization are used as the donor units,two conjugated polymers were synthesized.The quinone structure is conducive to the redshift of absorption and fluores-cence spectra,and the sp3 hybridization structure is conducive to weakening the aggregation quenching of polymer fluorescence.PF and PCz exhibited absorption peaks of 492 nm and 508 nm,respectively.The emission peaks of the two polymers are 920 nm and 950 nm,respec-tively,both in the short-wave near infrared region.The quantum yield(QY)of PF and PCz is 0.4%and 0.3%,respectively.展开更多
Within a Su-Schriffer-Heeger model modified to include electron-electron interaction and an external electric field, we investigate the dynamics of oppositely charged polarons in a polymer chain in the presence of bot...Within a Su-Schriffer-Heeger model modified to include electron-electron interaction and an external electric field, we investigate the dynamics of oppositely charged polarons in a polymer chain in the presence of both electron-phonon and electron-electron interactions under the influence of an external electric field. We adopt a multi-configurational time-dependent Hartree-Fock method for the time-dependent Schrodinger equation and the Newtonian equation of motion for a lattice. Our results show that the on-site Coulomb interaction is of fundamental importance and favors the recombination between the pairs of polarons, and the yield of excitons depends crucially on the strength of the on-site Coulomb interaction U. Furthermore, the influence of the nearest neighbor interaction V is also discussed.展开更多
Donor-acceptor(D-A)conjugated polymers are widely used in photovoltaic applications and heteroge-neous catalysis due to their tunable building block and pre-designable structures.Here,a series of ad-justable Donor-acc...Donor-acceptor(D-A)conjugated polymers are widely used in photovoltaic applications and heteroge-neous catalysis due to their tunable building block and pre-designable structures.Here,a series of ad-justable Donor-acceptor(D-A)benzothiodiazole-based conjugated polymers were designed and synthe-sized.The photocatalytic performance could be improved by fine-tuning the chemical structure by halo-gen substitution(F or Cl).The polymers exhibited excellent optoelectronic properties and were effective photocatalysts for the degradation of RhB and MO dyes,as well as promoting the oxidative coupling of benzylamines.Complete degradation of RhB and MO occurred in 30 min under visible light radiation,while the yield of benzylamine coupling mediated by superoxide anion was as high as 82%.Systematic characterization methods were used to gain insights on the unique photocatalytic performance of the polymers.Our findings provide further insights into the design and synthesis of benzothiadiazole-based conjugated polymers as promising organic photocatalysts for solar energy conversion.展开更多
Benzothiadiazole(BT)is an electron-deficient unit with fused aromatic core,which can be used to construct conjugated polymers for application in organic solar cells(OSCs).In the past twenty years,huge numbers of conju...Benzothiadiazole(BT)is an electron-deficient unit with fused aromatic core,which can be used to construct conjugated polymers for application in organic solar cells(OSCs).In the past twenty years,huge numbers of conjugated polymers based on BT unit have been developed,focusing on the backbone engineering(such as by using different copolymerized building blocks),side chain engineering(such as by using linear or branch side units),using heteroatoms(such as F,O and S atoms,and CN group),etc.These modifications enable BT-polymers to exhibit distinct absorption spectra(with onset varied from 600 nm to 1000 nm),different frontier energy levels and crystallinities.As a consequence,BT-polymers have gained much attention in recent years,and can be simultaneously used as electron donor and electron acceptor in OSCs,providing the power conversion efficiencies(PCEs)over 18%and 14%in non-fullerene and all-polymer OSCs.In this article,we provide an overview of BT-polymers for OSCs,from donor to acceptor,via selecting some typical BT-polymers in different periods.We hope that the summary in this article can invoke the interest to study the BT-polymers toward high performance OSCs,especially with thick active layers that can be potentially used in large-area devices.展开更多
基金financially supported by the Sichuan Science and Technology Program(2022YFS0025 and 2024YFFK0133)supported by the“Fundamental Research Funds for the Central Universities of China.”。
文摘Tactile perception plays a vital role for the human body and is also highly desired for smart prosthesis and advanced robots.Compared to active sensing devices,passive piezoelectric and triboelectric tactile sensors consume less power,but lack the capability to resolve static stimuli.Here,we address this issue by utilizing the unique polarization chemistry of conjugated polymers for the first time and propose a new type of bioinspired,passive,and bio-friendly tactile sensors for resolving both static and dynamic stimuli.Specifically,to emulate the polarization process of natural sensory cells,conjugated polymers(including poly(3,4-ethylenedioxythiophen e):poly(styrenesulfonate),polyaniline,or polypyrrole)are controllably polarized into two opposite states to create artificial potential differences.The controllable and reversible polarization process of the conjugated polymers is fully in situ characterized.Then,a micro-structured ionic electrolyte is employed to imitate the natural ion channels and to encode external touch stimulations into the variation in potential difference outputs.Compared with the currently existing tactile sensing devices,the developed tactile sensors feature distinct characteristics including fully organic composition,high sensitivity(up to 773 mV N^(−1)),ultralow power consumption(nW),as well as superior bio-friendliness.As demonstrations,both single point tactile perception(surface texture perception and material property perception)and two-dimensional tactile recognitions(shape or profile perception)with high accuracy are successfully realized using self-defined machine learning algorithms.This tactile sensing concept innovation based on the polarization chemistry of conjugated polymers opens up a new path to create robotic tactile sensors and prosthetic electronic skins.
基金supported by National Natural Science Foundation of China(22171041,22071020,52130101)National Key R&D Program of China(2023YFB3003001)+2 种基金Natural Science Foundation of Jilin Province Science and Technology Department(discipline layout project)(grant no.20230508094RC)the Fundamental Research Funds for the Central Universities(grant no.2412021QD008)the Fundamental Research Funds for the Central Universities-Excellent Youth Team Program(2412023YQ001).
文摘In conjugated polymers(CPs)photocatalytic system,the generation of reactive oxygen species(ROS)is regulated by cross-scale factors involving active site,excitonic behavior,and O_(2)activation process on the surface.However,research on exploring the domino effect of“structure→excitonic behavior→O_(2)activation→photocatalytic reaction”through structural modification at the atomic scale remains at its early stages.Herein,two heptazine-based CPs,CP-DPA,and CP-CZ were successfully prepared by polymerization of precursors formed by reacting diphenylamine(DPA)and carbazole(CZ)with cyameluric chloride,respectively.The minute difference in single bond between DPA and CZ endows the polymers with distinct physicochemical properties.Owing to the rotation between benzene rings,CP-DPA exhibits relatively lower conjugation,resulting in increased exciton binding energy(Eb)and inhibited exciton dissociation.Meanwhile,its more triplet state excitons facilitate energy transfer to generate singlet oxygen.Therefore,CP-DPA shows excellent activity for phenylboronic acid oxidation.Conversely,CP-CZ possesses relatively higher conjugation,minimal Eb and intensified exciton dissociation,which promotes charge transfer to produce superoxide radical.Consequently,CP-CZ displays optimal activity for phe-nylacetylene oxidation and[3+2]cycloaddition.This work provides new insights into regulating ROS gener-ation by modulating the composition and structure of photocatalysts at the atomic scale.
基金Khalifa University,Abu Dhabi,for the generous support of this researchthe financial support from the Khalifa University Research&Innovation Grant(RIG-2023-005)。
文摘Conjugated polymers(CPs)have emerged as an interesting class of materials in modern electronics and photonics,characterized by their unique delocalizedπ-electron systems that confer high flexibility,tunable electronic properties,and solution processability.These organic polymers present a compelling alternative to traditional inorganic semiconductors,offering the potential for a new generation of optoelectronic devices.This review explores the evolving role of CPs,exploring the molecular design strategies and innovative approaches that enhance their optoelectronic properties.We highlight notable progress toward developing faster,more efficient,and environmentally friendly devices by analyzing recent advancements in CP-based devices,including organic photovoltaics,field-effect transistors,and nonvolatile memories.The integration of CPs in flexible sustainable technologies underscores their potential to revolutionize future electronic and photonic systems.As ongoing research pushes the frontiers of molecular engineering and device architecture,CPs are poised to play an essential role in shaping next-generation technologies that prioritize performance,sustainability,and adaptability.
基金supported by the Natural Science Foundation of China(22408278,22275139,21971190,U21A2077)the Key Project of Natural Science Foundation of Tianjin City(Contract No.22JCZDJC00510)Key Laboratory of Functional Inorganic Material Chemistry(Heilongjiang University),Ministry of Education。
文摘Solar-driven hydrogen peroxide(H_(2)O_(2))production offers a sustainable and environmentally friendly alternative to the traditional anthraquinone oxidation method.Conjugated polymers(CPs)are emerging as promising photocatalysts for H_(2)O_(2)production due to their unique electronic,optical properties,and tunable structures.However,the high exciton binding energy of CPs hinders efficient exciton dissociation and charge separation,limiting their photocatalytic performance.In this work,we synthesized scandium(Sc)atoms decorated CPs with enhanced ordered stacking and crystallinity by introducing benzaldehyde as an end-capping reagent.The strong interaction between charged Sc atoms and electrons facilitates exciton dissociation and improves charge transfer capability.Furthermore,the Lewis acidic nature of Sc atoms promotes oxygen adsorption and enhances the stabilization of superoxide anion intermediate(·O_(2)^(-)).As a result,the as-synthesized photocatalysts exhibit a high H_(2)O_(2)production rate of 18μmol h^(-1)in pure water,which is three times that of pristine CPs,This work provides valuable insights into the design of organic polymer photocatalysts for various photocatalytic reactions.
基金This study was financially supported by Beijing Natural Science Foundation of China.(No.JQ21006)the National Natural Science Foundation of China(Nos.92163128,52073016,51773207,21905018 and 21905158)of China+2 种基金This work was further financially supported by the Fundamental Research Funds for the Central Universities(Nos.buctrc201828 and XK1802-2)the opening Foundation of State Key Laboratory of Organic-Inorganic Composites,Beijing University of Chemical Technology(No.oic-202201006)Jiangxi Provincial Department of Science and Technology(No.20192ACB20009).
文摘In this work,the“functionalization-polymerization”(FP)method has been used to construct fullerene-contained double-cable conjugated polymers with“donor-acceptor”backbones.It was realized via synthesizing a fullerene-contained monomer and performing Stille polymerization.With this method,a series of double-cable conjugated polymers with different fullerene contents were developed and applied into single-component organic solar cells.The power conversion efficiencies(PCEs)based on these polymers increased from 0.71%to 1.71%with the enhanced fullerene contents.The relatively low PCEs might be originated from the poor microstructure in these polymers.These new conjugated polymers with molecular heterojunction would show potential application in organic electronic devices.
基金the financial support from 985/211 Project(No.WF220411002)Shanghai Jiao Tong University and the national "1000-talent Plan(Youth)"
文摘Exploring the charge transport properties and electronic functions of molecules is of primary interest in the area of molecular electronics.Conjugated polymers（CPs） represent an attractive class of molecular candidates,benefiting from their outstanding optoelectronic properties.However,they have been less studied compared with the small-molecule family,mainly due to the difficulties in incorporating CPs into molecular junctions.In this review,we present a summary on how to fabricate CP-based singlechain and monolayered junctions,then discuss the transport behaviors of CPs in different junction architectures and finally introduce the potential applications of CPs in molecular-scale electronic devices.Although the research on CP-based molecular electronics is still at the initial stage,it is widely accepted that（1） CP chains are able to mediate long-range charge transport if their molecular electronic structures are properly designed,which makes them potential molecular wires,and（2） the intrinsic optoelectronic properties of CPs and the possibility of incorporating desirable functionalities by synthetic strategies imply the potential of employing tailor-made polymeric components as alternatives to small molecules for future molecular-scale electronics.
基金financially supported by the National Natural Science Foundation of China(Nos.21574144,51273209 and 51411140244)Zhejiang Provincial Natural Science Foundation of China(No.LR16B040002)+1 种基金CAS Interdisciplinary Innovation Team and Ningbo Municipal Science and Technology Innovative Research Team(Nos.2015B11002 and 2016B10005)Ningbo Natural Science Foundation(No.2016A610277)
文摘Development of organic semiconductors is one of the most intriguing and productive topics in material science and engineering. Many efforts have been made on the synthesis of aromatic building blocks such as benzene, thiophene and pyrrole due to the facile preparation accompanied by the intrinsic environmental stability and relatively efficient properties of the resulting polymers. In the past, furan has been less explored in this field because of its high oxidation potential. Recently, furan has attracted obsession due to its weaker aromaticity, the greater solubilities of furan-containing π-conjugated polymers relative to other benzenoid systems and the accessibility of furan-based starting materials from renewable resources. This review elaborates the advancements of organic photovoltaic polymers containing furan building blocks. The uniqueness and advantages of furan-containing building blocks in semiconducting materials are also discussed.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea Government(MSIT)(No.NRF-2021R1A2C2004109)the Korea Institute for Advancement of Technology(KIAT)grant funded by the Korea Government(MOTIE)(No.P0020612,2022 The Competency Development Program for Industry Specialist).
文摘Wearable biosensors have received great interest as patient-friendly diagnostic technologies because of their high flexibility and conformability.The growing research and utilization of novel materials in designing wearable biosensors have accelerated the development of point-of-care sensing platforms and implantable biomedical devices in human health care.Among numerous potential materials,conjugated polymers(CPs)are emerging as ideal choices for constructing high-performance wearable biosensors because of their outstanding conductive and mechanical properties.Recently,CPs have been extensively incorporated into various wearable biosensors to monitor a range of target biomolecules.However,fabricating highly reliable CP-based wearable biosensors for practical applications remains a significant challenge,necessitating novel developmental strategies for enhancing the viability of such biosensors.Accordingly,this review aims to provide consolidated scientific evidence by summarizing and evaluating recent studies focused on designing and fabricating CP-based wearable biosensors,thereby facilitating future research.Emphasizing the superior properties and benefits of CPs,this review aims to clarify their potential applicability within this field.Furthermore,the fundamentals and main components of CP-based wearable biosensors and their sensing mechanisms are discussed in detail.The recent advancements in CP nanostructures and hybridizations for improved sensing performance,along with recent innovations in next-generation wearable biosensors are highlighted.CPbased wearable biosensors have been—and will continue to be—an ideal platform for developing effective and user-friendly diagnostic technologies for human health monitoring.
基金supported by the National Natural Science Foundation of China(Nos.21774015 and 21975027)NSFC-MAECI(No.51861135202).
文摘In principle,conjugated polymers can work as electron donors and thus as low-cost p-type organic semiconductors to transport holes in photovoltaic devices.With the booming interests in high-efficiency and low-cost solar cells to tackle global climate change and energy shortage,hole transporting materials(HTMs)based on conjugated polymers have received increasing attention in the past decade.In this perspective,recent advances in HTMs for a range of photovoltaic devices including dye-sensitized solar cells(DSSCs),perovskite solar cells(PSCs),and silicon(Si)/organic heterojunction solar cells(HSCs)are summarized and perspectives on their future development are also presented.
基金financially supported by the Russian Foundation for Basic Research(GFEN_a No.12-03-91175)the National Natural Science Foundation of China(No.51211120187)
文摘Four new low-band-gap alternating copolymers （P-1, P-2, P-3 and P-4） based on electron-rich benzodithiophene and newly developed electron-deficient units, thienopyrazine or dithiadiazatrindene derivatives, were synthesized by Stille polycondensation. All polymers exhibit good solubility in common organic solvents and a broad absorption band in the visible to near-infrared regions. The film optical band gaps of the polymers are in the range of 1.28-2.07 eV and the highest occupied molecular orbital （HOMO） energy levels are in the range of-4.99 eV to -5.28 eV. Bulk heterojunction polymer solar cells （PSCs） of the polymers were fabricated with phenyl-C61-butyric acid methyl ester （PC61BM） as acceptor material, and a power conversion efficiency of 0.80% was realized with P-1 as donor material.
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the financial support from the National Natural Science Foundation of China(No. 21675106)the 111 Project(No. B14041)+2 种基金Natural Science Basic Research Plan in Shaanxi Province of China (No. 2017JM2019)the Program for Changjiang Scholars and Innovative Research Team in University (No. 14R33)the Program for Innovative Research Team in Shaanxi Province(No. 2014KCT-28)
文摘Herein, we reported a new label-free and fluorescence turn-on biosensor based on cationic conjugated poly（9,9-bis（6＇-N,N,N-trimethylammonium）hexyl）fluorine phenylene）（PFP） and perylene diimide derivatives（PDI）. Cationic PFP, single-stranded nucleic acid and PDI were used as signal reporter, probe and fluorescence quencher, respectively. In the presence of nucleic acids, they form complexes with PFP and PDI through strong electrostatic attraction interactions, resulting in PDI aggregating on nucleic acids and fluorescence of PFP being quenched. When nucleic acids are hydrolyzed by enzymes or their conformation is changed via recognizing targets, the effective aggregation of PDI is disrupted and the quenching ability is decreased. Thus the fluorescence of PFP recovers significantly. By taking advantage of the mechanism, we construct a new biosensor for endonuclease and small molecules detection. Here, S1 nuclease and bisphenol A are used as model systems. The detection limit of the SI nuclease and BPA are1.0×10^-6U/mL and 0.05 ng/mL, respectively. Our method is sensitive, cost-effective and simple, and provides a new platform for bioanalysis.
基金financially supported by the National Natural Science Foundation of China(Nos.22135007,21875244 and 52073281)Jilin Scientific and Technological Development Program(No.YDZJ202101ZYTS138)。
文摘The development of donor-acceptor(D-A)type conjugated polymers depends largely on the design of novel A building blocks.Herein,we report a novel A building block based on the cyano-substituted organoboron unit(SBN-3).Compared with the most common fluorine-substituted B←N unit,SBN-3 displays a significantly downshifted LUMO energy level because of the strong electron-withdrawing ability of cyano groups.In addition,due to the greater impact of cyano substitution on LUMO than on HOMO,SBN-3 exhibits a reduced band gap,nearinfrared absorption and fluorescence properties.The D-A type conjugated polymers based on the cyano-substituted B←N unit with thiophene-based units show narrow optical band gaps of ca.1.3 e V as well as distinctive electronic structures,i.e.,delocalized LUMOs and localized HOMOs.This work thus provides not only an effective approach to design strong A units but also a new electron-deficient building block for D-A type conjugated polymers.
基金the financial supports of the National Natural Science Foundation of China(Nos 50803040 and 20872103)and Analytical & Testing Center of Sichuan University for NMR measurements
文摘Three novel conjugated polymers bearing 3,4-bis（4-hexylthiophen-2-yl）-3-cyclobutene-1,2-dione unit in their main chain have been synthesized successfully in good yields through Suzuki or Stille coupling reaction.Their molecular structures have been confirmed by FT-IR,~1H NMR and ^（13）C NMR.All these copolymers exhibit broad and strong absorption bands in UV-vis region,and their optical band gaps are calculated to be 1.6-2.0 eV.suggesting that they have good coverage with the solar spectrum.These polymers have good thermostability and solubility in common organic solvents.Moreover,all these objective macromolecules possess high electron affinity of～3.8 eV determined from cyclic voltammetry measurement,implying that they are potential n-type polymeric photovoltaic materials.
基金the National Natural Science Foundation of China(Nos.22075271,21625403,21875244 and 21875241)B.M.thanks the financial supports by State Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences and the Jilin Scientific and Technological Development Program(No.20220508142RC).
文摘The development of n-type polymer thermoelectrics lags far behind that of p-type ones in view of material diversity and performance.New structural insights into the thermoelectric performance are needed for efficient n-type polymer thermoelectric materials.Herein,we developed three acceptor-acceptor type organoboron polymers and investigated the effect of backbone configuration on thermoelectric performance.The three polymers are designed based on double B←N bridged bipyridine(BNBP)unit with monomeric thieno[3,4-c]pyrrole-4,6-dione(TPD),TPD dimer and TPD trimer as the copolymerizing units,respectively.The three polymers show similar low LUMO energy levels but different backbone configuration.Compared with the wavy backbone configuration,the pseudo-straight backbone configuration imparts the polymer with much enhanced crystallinity and electron mobility.As a result,after n-doping,the polymer with pseudo-straight configuration shows much higher electronic conductivity and power factor.We think these findings could serve as important guidelines for molecular design toward efficient n-type polymer thermoelectric materials.
基金jointly supported by the Beijing Natural Science Foundation (Nos.2212045 and JQ21006)the National Natural Science Foundation of China (Nos.21905158, 52073016 and 92163128)+2 种基金further supported by the Fundamental Research Funds for the Central Universities (Nos.buctrc202111, buctrc201828, and XK1802-2)the Opening Foundation of State Key Laboratory of Organic-Inorganic Composites of Beijing University of Chemical Technology (No.oic-202201006)Jiangxi Provincial Department of Science and Technology (Nos.20202ACBL213004, 20212BCJ23035, jxsq2019102004)。
文摘The photovoltaic properties of double-cable conjugated polymers are significantly influenced by the length of the alkyl linkers that connect donor backbones and acceptor side units. In this study, a series of 2-(3-oxo-2,3-dihydroinden-1-ylidene)malononitrile(IC)-based double-cable polymers with alkyl linkers ranging from C_8H_(16)to C_(16)H_(32)(Px, x = 8, 10, 12, 14, 16) were synthesized for single-component organic solar cells(SCOSCs). Among these, the linker length x = 12(P12) is found to optimize the power conversion efficiencies(PCEs) in SCOSCs. Specifically, PCEs increase from P8 to P12 and then decline from P12to P16. Detailed investigations of optical absorption, charge transport, and morphology provide insights into the underlying factors contributing to these PCE variations. The findings indicate that the exceptional photovoltaic properties observed in P12 can be attributed to three key factors: A delicate balance between enhanced charge separation facilitated by the increased spacer length and reduced crystallinity resulting from longer spacers, higher charge mobilities, and well-balanced hole/electron transport characteristics. This study highlights the critical role of linker length in determining the photovoltaic properties of double-cable conjugated polymer-based SCOSCs and offers valuable guidance for the design of novel double-cable conjugated polymers.
基金supported by the National Natural Science Foundation of China(Grant Nos.21807062 and 21976099)the Shandong Provincial Natural Science Foundation(ZR2018BB014)+3 种基金the Department of Science and Technology of Shan-dong Province(2019GGX102020)the Source In-novation Project of Qingdao(171183jch)Qingdao Postdoctoral Applied Research Project(2018111)National College Students Innovation and En-trepreneurship Training Program(201910429007)
文摘The absorption,scattering,and autofluorescence of biological tissues in short-wave infrared re-gion(SWIR,900-1700 nm)are relatively low,so SWIR fluorescence usually has deeper pene-tration into living tissues,and can show a higher signal-to-noise ratio when used for imaging in vivo.However,there are few types of organic SWIR fluorescent materials currently.In this work,p-azaquinodimethane(p-AQM)with a quinoid structure is used as the acceptor unit,and car-bazole or fluorene with sp3 hybridization are used as the donor units,two conjugated polymers were synthesized.The quinone structure is conducive to the redshift of absorption and fluores-cence spectra,and the sp3 hybridization structure is conducive to weakening the aggregation quenching of polymer fluorescence.PF and PCz exhibited absorption peaks of 492 nm and 508 nm,respectively.The emission peaks of the two polymers are 920 nm and 950 nm,respec-tively,both in the short-wave near infrared region.The quantum yield(QY)of PF and PCz is 0.4%and 0.3%,respectively.
基金Supported by the National Natural Science Foundation of China under Grant No 11474218
文摘Within a Su-Schriffer-Heeger model modified to include electron-electron interaction and an external electric field, we investigate the dynamics of oppositely charged polarons in a polymer chain in the presence of both electron-phonon and electron-electron interactions under the influence of an external electric field. We adopt a multi-configurational time-dependent Hartree-Fock method for the time-dependent Schrodinger equation and the Newtonian equation of motion for a lattice. Our results show that the on-site Coulomb interaction is of fundamental importance and favors the recombination between the pairs of polarons, and the yield of excitons depends crucially on the strength of the on-site Coulomb interaction U. Furthermore, the influence of the nearest neighbor interaction V is also discussed.
基金financially supported by National Natural Science Foundation of China(No.52173099)the Science and Technology Department of Jiangxi Province(No.20192BBEL50025)+1 种基金Nanchang Hangkong University(No.EA201902288)the Special Fund for Graduate Innovation(No.YC2020-011).
文摘Donor-acceptor(D-A)conjugated polymers are widely used in photovoltaic applications and heteroge-neous catalysis due to their tunable building block and pre-designable structures.Here,a series of ad-justable Donor-acceptor(D-A)benzothiodiazole-based conjugated polymers were designed and synthe-sized.The photocatalytic performance could be improved by fine-tuning the chemical structure by halo-gen substitution(F or Cl).The polymers exhibited excellent optoelectronic properties and were effective photocatalysts for the degradation of RhB and MO dyes,as well as promoting the oxidative coupling of benzylamines.Complete degradation of RhB and MO occurred in 30 min under visible light radiation,while the yield of benzylamine coupling mediated by superoxide anion was as high as 82%.Systematic characterization methods were used to gain insights on the unique photocatalytic performance of the polymers.Our findings provide further insights into the design and synthesis of benzothiadiazole-based conjugated polymers as promising organic photocatalysts for solar energy conversion.
基金financially supported by the Ministry of Science and Technology(Nos.2018YFA0208504 and 2017YFA0204702)the National Natural Science Foundation of China(Nos.51773207,52073016,and 21905018)+2 种基金supported by Fundamental Research Funds for the Central Universities(No.XK1802-2)Jiangxi Provincial Department of Science and Technology(No.20192ACB20009)the Natural Science Foundation of Hebei Province(No.B2020201032)。
文摘Benzothiadiazole(BT)is an electron-deficient unit with fused aromatic core,which can be used to construct conjugated polymers for application in organic solar cells(OSCs).In the past twenty years,huge numbers of conjugated polymers based on BT unit have been developed,focusing on the backbone engineering(such as by using different copolymerized building blocks),side chain engineering(such as by using linear or branch side units),using heteroatoms(such as F,O and S atoms,and CN group),etc.These modifications enable BT-polymers to exhibit distinct absorption spectra(with onset varied from 600 nm to 1000 nm),different frontier energy levels and crystallinities.As a consequence,BT-polymers have gained much attention in recent years,and can be simultaneously used as electron donor and electron acceptor in OSCs,providing the power conversion efficiencies(PCEs)over 18%and 14%in non-fullerene and all-polymer OSCs.In this article,we provide an overview of BT-polymers for OSCs,from donor to acceptor,via selecting some typical BT-polymers in different periods.We hope that the summary in this article can invoke the interest to study the BT-polymers toward high performance OSCs,especially with thick active layers that can be potentially used in large-area devices.
