A series of linear and X-shaped oligo（para-phenylene） derivatives functionalized with fluorene ethynylenes 1,3 and 4 were synthesized through sequent Sonogashira coupling and Suzuki-Miyaura reaction in high yield.Th...A series of linear and X-shaped oligo（para-phenylene） derivatives functionalized with fluorene ethynylenes 1,3 and 4 were synthesized through sequent Sonogashira coupling and Suzuki-Miyaura reaction in high yield.The electron-donating group-OCH3 and electron-withdrawing counterparts-CF3 were introduced to tune the spectra properties of compounds 3 and 4.The detail investigation of their photophysical properties in solution and film indicated that the introduction of both -OCH3 and -CF3 makes maximum emission distinct red-shift in comparison with parent compound 1,but the latter more prominently.展开更多
A first-principles computational method based on the hybrid density functional theory is developed to simulate the electronic transport properties of oligomeric phenylene ethynylene molecular junctions with H2O molecu...A first-principles computational method based on the hybrid density functional theory is developed to simulate the electronic transport properties of oligomeric phenylene ethynylene molecular junctions with H2O molecules accumulated in the vicinity as recently reported by Na et al. [Nanotechnology 18 424001 （2007）]. The numerical results show that the hydrogen bonds between the oxygen atoms of the oligomeric phenylene ethynylene molecule and H2O molecules result in the localisation of the molecular orbitals and lead to the lower transition peaks. The H2O molecular chains accumulated in the vicinity of the molecular junction can not only change the electronic structure of the molecular junctions, but also open additional electronic transport pathways. The obvious influence of H2O molecules on the electronic structure of the molecular junction and its electronic transport properties is thus demonstrated.展开更多
Poly（phenylene ethynylene）s （P1） with 4-vinylaniline pendant groups were successfully prepared by the Sonogashira coupling polymerization bevween 1,4-diethynyl-2,5-bis（pentyloxy）benzene and 4-[2-（2,5-dibromophe...Poly（phenylene ethynylene）s （P1） with 4-vinylaniline pendant groups were successfully prepared by the Sonogashira coupling polymerization bevween 1,4-diethynyl-2,5-bis（pentyloxy）benzene and 4-[2-（2,5-dibromophenyl）vinyl]- aniline. In comparison with its analogue P2 without amino group, the emission of F＇I is only enihanced by aggregation when adding n-hexane into its THF solution, exhibiting an aggregation-induced emission enhancement （AIEE） effect. When methanol or water instead of hexane was added into THF solution, P1, however, didn＇t show AII：~E. The results indicated that amino groups strengthen the inter-chain and intra-chain interactions in P1 and restrict the no^-radiative energy transition. This strategy can provide a platform for developing highly sensitive and efficient bio- and chemosensors.展开更多
A series of linear and V-shaped oligo(phenylene ethynylene) derivatives 1-3 were synthesized through sequent Sonogashira coupling and propargyl alcohol deprotection reaction in high yields.The alkoxy chains(i.e.,n-hex...A series of linear and V-shaped oligo(phenylene ethynylene) derivatives 1-3 were synthesized through sequent Sonogashira coupling and propargyl alcohol deprotection reaction in high yields.The alkoxy chains(i.e.,n-hexyloxy groups) were introduced to assure good solubility of compounds 1-3 in common solvents.The photophysical properties of 1-3 in solution depend strongly on the geometries of these compounds.展开更多
Novel n-conjugated polymers constituted of 2,1,3-benzothiadiazole or cyano-containing unit copolymers were synthesized and characterized by UV-Vis, IR and PL.
Separator modification represents a critical strategy for addressing the challenges in lithium-ion batteries(LIBs),including restricted Li^(+) transport,poor interfacial stability,and safety risks.Using functional coa...Separator modification represents a critical strategy for addressing the challenges in lithium-ion batteries(LIBs),including restricted Li^(+) transport,poor interfacial stability,and safety risks.Using functional coatings has emerged as an effective approach for enhancing separator performance without altering the bulk structure of the separators.Herein,we report the first example of ethynylene-linked conjugated microporous polymers(CMPs)for LIB separator modification.Specifically,two CMPs substituted with different groups(fluorine for CMP-F and methyl for CMP-CH_(3))were synthesized through dynamic alkyne metathesis and applied as functional coatings on polyethylene(PE)separators.The ethynylene-linked backbone structure,along with the introduction of electron-withdrawing fluorine atoms,endows the CMPs with high electron density,hence reducing Li^(+) binding and solvent interactions,lowering the desolvation energy barrier at the electrolyte-separator interface,and facilitating Li^(+) transport.The fluorine could also act as hopping sites to facilitate Li^(+) conduction.We demonstrated through full-cell evaluations using graphite anodes and NMC532 cathodes that CMP-F@PE separators significantly improve both the rate performance and cycling stability.Furthermore,the CMP-F@PE separators also exhibited outstanding thermal stability,thereby improving battery safety.These results highlight the great potential of ethynylene-linked CMPs as structurally tunable,superior-performance,high-efficiency separator coatings for next-generation LIBs.展开更多
Introducing ethynylene linkages in a conjugated molecule can deepen the HOMO level, decrease the steric con- straints and better delocalize the n electrons and so on, which are beneficial for organic solar cells. Furt...Introducing ethynylene linkages in a conjugated molecule can deepen the HOMO level, decrease the steric con- straints and better delocalize the n electrons and so on, which are beneficial for organic solar cells. Furthermore, the typical method of introducing acetylene linkages by Sonogashira reactions can avoid the usage of toxic stannyl in- termediates and potentially dangerous lithiation reactions. In this study, two simple small molecules BEDPP and NEDPP are designed and synthesized, in which two diketopyrrolopyrrole units are symmetrically connected to benzene and naphthalene cores, respectively, via acetylene linkages. And the BHJ （Bulk Heterojunction） solar cells based on BEDPP and NEDPP without using solvent additive and without any post-treatment for the active layers provide us power conversion efficieneies of 1.48% and 2.31% with remarkably high open circuit voltages up to 0.90 and 0.98 V, respectively.展开更多
Two copolymers of P1 and P2 comprising benzothiadiazole, 1,4-bis（dodecyloxy）-benzene units were synthesized by Sonogashira coupling polymerization based on ethynyl-linked 1,2,5,6-naphthalenediimide. Their thermal, o...Two copolymers of P1 and P2 comprising benzothiadiazole, 1,4-bis（dodecyloxy）-benzene units were synthesized by Sonogashira coupling polymerization based on ethynyl-linked 1,2,5,6-naphthalenediimide. Their thermal, optical, electrochemical as well as charge transport properties were studied. Bottom-gate top-contact organic field-effect transistors （OFETs） measurements of P1 and P2 thin films showed different charge transport behaviors. P1 displayed pure electron transport behaviors in OFETs with electron mobility up to 10^-3 cm^2·V-1·s^-1, while P2 exhibited hole transport features. The molecular structure analysis revealed that the structure of P1 has the acceptor-linker-acceptor＇ （A-L-A＇） characteristic, and P2 possesses the donor-linker-acceptor （D-L-A） structure feature. The results demonstrate that different molecular structures lead them to have distinct charge transport behaviors. In particular, the first pure electron transport copolymer in OFETs based on 1,2,5,6-naphthalenediimide is achieved.展开更多
A library of rod-like bolapolyphiles with sticky hydrogen-bonded glycerol groups at their ends and having highly branched side chains with a carbosilane-based four-way branching point,all based on the same oligo(pheny...A library of rod-like bolapolyphiles with sticky hydrogen-bonded glycerol groups at their ends and having highly branched side chains with a carbosilane-based four-way branching point,all based on the same oligo(phenylene ethynylene)core,has been synthesized and investigated.For these compounds,a A15-type Frank–Kasper phase is formed upon side-chain elongation in the steric frustration range at the transition from the triangular to the much larger square honeycombs.In contrast to the previously known tetrahedral sphere packings the A15 phase is in this case formed by tetrahedral networks of aggregates of parallelly organizedπ-conjugated rods.This allows the design of compounds with wide ranges of the A15 network down to room temperature.However,its formation becomes strongly disfavored by core fluorination that is attributed to a changing mode of core–core interaction that also modifies the square honeycombs by deformation of the squares into rectangular or rhombic cells,either with or without emergence of tilt of the rods.展开更多
Tremendous interest has been evoked in the utility of the fluorescent conjugated polymers towards the creation of ultra-sensitive systems based on the molecular wire effects which can amplify the transduction events. ...Tremendous interest has been evoked in the utility of the fluorescent conjugated polymers towards the creation of ultra-sensitive systems based on the molecular wire effects which can amplify the transduction events. Here, a series of new polymers pyridine substitute poly (phen- ylene ethynylene)s are synthesized by Sonogashira-Hagihara coupling reaction. The impact of structure modification on the physical properties and spectral characteristics of poly-mers has been investigated. The quenching studies are car-ried out and exhibit that recognition site (pyridyle group) highly influences the quenching efficiency. The results show that polymer PI with pyridyl group entrapped in the conju-gated backbone has the specific and sensitive response to Pd(Ⅱ). The fluorescence quenching of PⅠby Pd(Ⅱ) is about 65 times greater than that of model monomer.展开更多
基金Beijing Natural Science Foundation(No.2093033)Scientific Research Project of Beijing Educational Committee(Nos.KM 200910020012 and KM 201010020002) for financial support
文摘A series of linear and X-shaped oligo（para-phenylene） derivatives functionalized with fluorene ethynylenes 1,3 and 4 were synthesized through sequent Sonogashira coupling and Suzuki-Miyaura reaction in high yield.The electron-donating group-OCH3 and electron-withdrawing counterparts-CF3 were introduced to tune the spectra properties of compounds 3 and 4.The detail investigation of their photophysical properties in solution and film indicated that the introduction of both -OCH3 and -CF3 makes maximum emission distinct red-shift in comparison with parent compound 1,but the latter more prominently.
基金Project supported by the National Natural Science Foundation of China (Grant Nos.10804064 and 10674084)
文摘A first-principles computational method based on the hybrid density functional theory is developed to simulate the electronic transport properties of oligomeric phenylene ethynylene molecular junctions with H2O molecules accumulated in the vicinity as recently reported by Na et al. [Nanotechnology 18 424001 （2007）]. The numerical results show that the hydrogen bonds between the oxygen atoms of the oligomeric phenylene ethynylene molecule and H2O molecules result in the localisation of the molecular orbitals and lead to the lower transition peaks. The H2O molecular chains accumulated in the vicinity of the molecular junction can not only change the electronic structure of the molecular junctions, but also open additional electronic transport pathways. The obvious influence of H2O molecules on the electronic structure of the molecular junction and its electronic transport properties is thus demonstrated.
基金financially supported by the National Natural Scientific Foundation of China(Nos.51073026 and 21004004)the Specialized Research Fund for the Doctoral Program of Higher Education of China(Nos.2009110111003 l and 20101101120029)Excellent Young Scholars Research Fund of Beijing Institute of Technology(No.2009Y0914)
文摘Poly（phenylene ethynylene）s （P1） with 4-vinylaniline pendant groups were successfully prepared by the Sonogashira coupling polymerization bevween 1,4-diethynyl-2,5-bis（pentyloxy）benzene and 4-[2-（2,5-dibromophenyl）vinyl]- aniline. In comparison with its analogue P2 without amino group, the emission of F＇I is only enihanced by aggregation when adding n-hexane into its THF solution, exhibiting an aggregation-induced emission enhancement （AIEE） effect. When methanol or water instead of hexane was added into THF solution, P1, however, didn＇t show AII：~E. The results indicated that amino groups strengthen the inter-chain and intra-chain interactions in P1 and restrict the no^-radiative energy transition. This strategy can provide a platform for developing highly sensitive and efficient bio- and chemosensors.
基金Beijing Natural Science Foundation(No.2093033)Scientific Research Project of Beijing Educational Committee(No.KM200910020012) for financial support.
文摘A series of linear and V-shaped oligo(phenylene ethynylene) derivatives 1-3 were synthesized through sequent Sonogashira coupling and propargyl alcohol deprotection reaction in high yields.The alkoxy chains(i.e.,n-hexyloxy groups) were introduced to assure good solubility of compounds 1-3 in common solvents.The photophysical properties of 1-3 in solution depend strongly on the geometries of these compounds.
基金We are gratefully acknowledged financial support of this work by the National Natural Science Foundation of China （No.20274039）.
文摘Novel n-conjugated polymers constituted of 2,1,3-benzothiadiazole or cyano-containing unit copolymers were synthesized and characterized by UV-Vis, IR and PL.
文摘Separator modification represents a critical strategy for addressing the challenges in lithium-ion batteries(LIBs),including restricted Li^(+) transport,poor interfacial stability,and safety risks.Using functional coatings has emerged as an effective approach for enhancing separator performance without altering the bulk structure of the separators.Herein,we report the first example of ethynylene-linked conjugated microporous polymers(CMPs)for LIB separator modification.Specifically,two CMPs substituted with different groups(fluorine for CMP-F and methyl for CMP-CH_(3))were synthesized through dynamic alkyne metathesis and applied as functional coatings on polyethylene(PE)separators.The ethynylene-linked backbone structure,along with the introduction of electron-withdrawing fluorine atoms,endows the CMPs with high electron density,hence reducing Li^(+) binding and solvent interactions,lowering the desolvation energy barrier at the electrolyte-separator interface,and facilitating Li^(+) transport.The fluorine could also act as hopping sites to facilitate Li^(+) conduction.We demonstrated through full-cell evaluations using graphite anodes and NMC532 cathodes that CMP-F@PE separators significantly improve both the rate performance and cycling stability.Furthermore,the CMP-F@PE separators also exhibited outstanding thermal stability,thereby improving battery safety.These results highlight the great potential of ethynylene-linked CMPs as structurally tunable,superior-performance,high-efficiency separator coatings for next-generation LIBs.
文摘Introducing ethynylene linkages in a conjugated molecule can deepen the HOMO level, decrease the steric con- straints and better delocalize the n electrons and so on, which are beneficial for organic solar cells. Furthermore, the typical method of introducing acetylene linkages by Sonogashira reactions can avoid the usage of toxic stannyl in- termediates and potentially dangerous lithiation reactions. In this study, two simple small molecules BEDPP and NEDPP are designed and synthesized, in which two diketopyrrolopyrrole units are symmetrically connected to benzene and naphthalene cores, respectively, via acetylene linkages. And the BHJ （Bulk Heterojunction） solar cells based on BEDPP and NEDPP without using solvent additive and without any post-treatment for the active layers provide us power conversion efficieneies of 1.48% and 2.31% with remarkably high open circuit voltages up to 0.90 and 0.98 V, respectively.
基金financially supported by the National Natural Science Foundation of China(No.21674126)the"Strategic Priority Research Program"(No.XDB12010100)the Shanghai Science and Technology Committee(No.16JC1400603)
文摘Two copolymers of P1 and P2 comprising benzothiadiazole, 1,4-bis（dodecyloxy）-benzene units were synthesized by Sonogashira coupling polymerization based on ethynyl-linked 1,2,5,6-naphthalenediimide. Their thermal, optical, electrochemical as well as charge transport properties were studied. Bottom-gate top-contact organic field-effect transistors （OFETs） measurements of P1 and P2 thin films showed different charge transport behaviors. P1 displayed pure electron transport behaviors in OFETs with electron mobility up to 10^-3 cm^2·V-1·s^-1, while P2 exhibited hole transport features. The molecular structure analysis revealed that the structure of P1 has the acceptor-linker-acceptor＇ （A-L-A＇） characteristic, and P2 possesses the donor-linker-acceptor （D-L-A） structure feature. The results demonstrate that different molecular structures lead them to have distinct charge transport behaviors. In particular, the first pure electron transport copolymer in OFETs based on 1,2,5,6-naphthalenediimide is achieved.
基金supported by the Deutsche Forschungsgemeinschaft(Grant 436494874)National Natural Science Foundation of China(Grant 12204369)+1 种基金Science and Technology Agency of Shaanxi(Grant 2023-YBGY-459)China Postdoctoral Science Foundation(Grants 2022M712551 and 2023T160505).
文摘A library of rod-like bolapolyphiles with sticky hydrogen-bonded glycerol groups at their ends and having highly branched side chains with a carbosilane-based four-way branching point,all based on the same oligo(phenylene ethynylene)core,has been synthesized and investigated.For these compounds,a A15-type Frank–Kasper phase is formed upon side-chain elongation in the steric frustration range at the transition from the triangular to the much larger square honeycombs.In contrast to the previously known tetrahedral sphere packings the A15 phase is in this case formed by tetrahedral networks of aggregates of parallelly organizedπ-conjugated rods.This allows the design of compounds with wide ranges of the A15 network down to room temperature.However,its formation becomes strongly disfavored by core fluorination that is attributed to a changing mode of core–core interaction that also modifies the square honeycombs by deformation of the squares into rectangular or rhombic cells,either with or without emergence of tilt of the rods.
文摘Tremendous interest has been evoked in the utility of the fluorescent conjugated polymers towards the creation of ultra-sensitive systems based on the molecular wire effects which can amplify the transduction events. Here, a series of new polymers pyridine substitute poly (phen- ylene ethynylene)s are synthesized by Sonogashira-Hagihara coupling reaction. The impact of structure modification on the physical properties and spectral characteristics of poly-mers has been investigated. The quenching studies are car-ried out and exhibit that recognition site (pyridyle group) highly influences the quenching efficiency. The results show that polymer PI with pyridyl group entrapped in the conju-gated backbone has the specific and sensitive response to Pd(Ⅱ). The fluorescence quenching of PⅠby Pd(Ⅱ) is about 65 times greater than that of model monomer.
