Acrylate latex modified by vinyl triisopropoxy silane (C-1706) was synthesized by seeded emulsion polymerization with anionic emulsifier sodium dodecyl sulphonate(SDS) and nonionic emulsifier OP-10 as the multiple emu...Acrylate latex modified by vinyl triisopropoxy silane (C-1706) was synthesized by seeded emulsion polymerization with anionic emulsifier sodium dodecyl sulphonate(SDS) and nonionic emulsifier OP-10 as the multiple emulsifiers at (78±2) ℃. The effects of different factors, such as the emulsifier, C-1706 monomer and its feeding manner on the properties of acrylate latex modified by C-1706 were investigated. The particle size distribution and the structure, the configuration, the weather durability and stain resistance of copolymer latex were characterized by particle size analyzer, Fourier transform infrared spectroscopy (FT-IR), transmission electron microscope(TEM), scanning electron microscope(SEM) and ultraviolet aging instrument respectively. The results show that SDS to OP-10 as multiple emulsifiers can lead to coordinated efficiency, the optimal emulsifier dosage is 2.4%?3.2%(mass fraction), and the mass ratio of SDS to OP-10 is 1?1? 1?2. The seeded emulsion polymerization can effectively introduce a organic-siloxane bonding in a macromolecule inter polymer, and the obtained acrylate latex modified by organic-siloxane possesses narrow distribution of particle size with mean diameter of 51.8?76.6 nm and has the excellent properties in weather durability and stain-resistance especially.展开更多
Two n-butoxy-encapsulated dendritic thermally activated delayed fluorescent(TADF) emitters(namely O-D1 and O-D2) with the first-/second-generation carbazoledendrons are designed and synthesized via C—N coupling betwe...Two n-butoxy-encapsulated dendritic thermally activated delayed fluorescent(TADF) emitters(namely O-D1 and O-D2) with the first-/second-generation carbazoledendrons are designed and synthesized via C—N coupling between carbazoledendrons and 2,4,6-tris(4-bromophenyl)-1,3,5-triazine core.It is found that,compa red with the commo nly-used tert-butyl groups,the use of n-butoxy encapsulation groups can lead to smallersinglet-triplet energy gap for the dendrimers,producing stronger TADF effect together with faster reverse intersystem crossing process.Solution-processed TADF organic light-emitting diodes(OLEDs) utilizingalkoxy-encapsulated dendrimers O-D1 and O-D2 as emitters exhibitstate-of-the-art device efficiency withthe maximum external quantum efficiency up to 16.8% and 20.6%,respectively,which are ~1.6 and~2.0 times that of the tert-butyl-encapsulated counterparts.These results suggest that alkoxy encapsulation of the carbazole-based TADF dendrimers can be a promising approach for developing highly efficient emitters for solution-processed OLEDs.展开更多
An acrylate emulsion was modified by adding vinyltriisopropoxy silane （trade name C-1706）. By adding the multiple emulsifier which consists of an anionic emulsifier, sodium dodecyl benzene sulfonate （SDBS） and non...An acrylate emulsion was modified by adding vinyltriisopropoxy silane （trade name C-1706）. By adding the multiple emulsifier which consists of an anionic emulsifier, sodium dodecyl benzene sulfonate （SDBS） and nonionic emulsifier, octyl phenolic divinyl oxide （OP-10）, the acrylosilane microemulsion was synthesized by seeded emulsion polymerization. The influential factors including the kind and the adding amount of emulsifiers and the monomer variety of alkoxy silane and the added methods which influence on the properties of the microemulsion were investigated. It is found that SDBS and OP-10 as multiple emulsifiers with mass ratio of 1：1 and the adding amount of 2.5%-3.5% can act on co-effect for emulsion polymerization. The C-1706 possesses bulky isopropoxy substituent that can reduce hydrolysis reactivity during the polymerization process, so as to not only make the process smoothly but also advance the store stability of the emulsion. Moreover, the latter-addition mode of C-1706 can restrain its hydrolysis activity and polycondensation reaction during the polymerization process of the emulsion. The structure, the film cross section, the particle size and its distribution of the microemulsion were analyzed by the Fourier Transform Infrared Ray Spectrum （FTIR）, Scanning Electron Microscopy （SEM） and a particle size analyzer, respectively. The results show that the particle diameter of the modified microemulsion can be controlled between 50 and 70 nm and its film hardness is 7.3. Only adding 1.5% of C-1706 into the system of emulsion polymerization can apparently improve the weathering resistance of the microemulsion, which undergo degradation with chromatism（△E） is 1.6 after 3 600 hours of QUV-aging.展开更多
In this paper, we report an improved method for preparing 2--alkoxy 5 fluoro--3H --4--pyrimidone from 2--chloro--5--fluoro--3H--4--pyrimidone and sodium alkoxide under normal pressure at reflux temperature. Some new c...In this paper, we report an improved method for preparing 2--alkoxy 5 fluoro--3H --4--pyrimidone from 2--chloro--5--fluoro--3H--4--pyrimidone and sodium alkoxide under normal pressure at reflux temperature. Some new compounds were synthesized in higher yield by this method.展开更多
The rearrangement of α-substituted phenyl-α, α′-dimethoxypropanones (R1) was recently proved to he an [1, 3] siqmatropic migration of methoxy group by study of LFER, solvent effect, crossover experiment, and by ot...The rearrangement of α-substituted phenyl-α, α′-dimethoxypropanones (R1) was recently proved to he an [1, 3] siqmatropic migration of methoxy group by study of LFER, solvent effect, crossover experiment, and by other means. The rearrangement catalysed by trace of totuenesulfonic acid gave a negligible value of the Hammett reaction constant. Further experimental results show that the electronic effect of substituent on the aromatic ring for the rearrangement in neutral medium is much greater (Table 1). We propose sigmatropic migration展开更多
N,O-Spiroaminals have potential biological activities and abilities to modulate the physicochemical and pharmacokinetic properties of drug molecules.However,effective catalytic methods for the efficient construction o...N,O-Spiroaminals have potential biological activities and abilities to modulate the physicochemical and pharmacokinetic properties of drug molecules.However,effective catalytic methods for the efficient construction of N,O-spiroaminals are still limited to date.Herein,we report a novel 1,1,2-trifunctionalization of unactivated alkenes to rapidly and efficiently obtain a diverse array of architecturally intriguing N,O-spiroaminals.This methodology exhibits broad substrate scope,good functional group compatibility,and potential synthetic utility by a scale-up reaction,diverse product derivatizations and late-stage functionalization of complex biorelevant molecule.Notably,this transformation selectively allows for the formation of three new chemical bonds(C–O,C–C,and C–N)and one spiro quaternary carbon center across C-C double bonds.展开更多
Ag_(2)CO_(3)-promoted dehydroxymethylative fluorination of aliphatic alcohols has been achieved with Selectfluor as both oxidant and fluorine source.The reaction involvesβ-fragmentation of primary alkoxy radicals,fol...Ag_(2)CO_(3)-promoted dehydroxymethylative fluorination of aliphatic alcohols has been achieved with Selectfluor as both oxidant and fluorine source.The reaction involvesβ-fragmentation of primary alkoxy radicals,followed by the fluorination of the resulting C-centered radical intermediates.The transformation proceeds under mild reaction conditions and exhibits a broad substrate scope,thus opening up a new entrance to the synthesis of fluorinated constructs includingα-fluoroimides and 1-fluoroalkyl benzoates as well as secondary and tertiary alkyl fluorides like versatile 2-fluoro-2-alkyl 1,3-propandiol derivatives.The divergent functionalization of the obtainedα-fluoroimides enables an efficient access to amine derivatives through C-F bond activation under the action of BF_(3)·OEt_(2).展开更多
A new approach for radical cross coupling of organic halides and oxalates toward esters has been developed via photoredox nickel dual catalysis.This method has been demonstrated for transformation of a wide range of a...A new approach for radical cross coupling of organic halides and oxalates toward esters has been developed via photoredox nickel dual catalysis.This method has been demonstrated for transformation of a wide range of aryl,heteroaryl,alkenyl,and alkyl bromides to various esters under mild conditions.Notably,fluoro-,chloro-,or iodo-substituents on the aryl bromides remain after the coupling reaction,which has been applied for the easy synthesis of drug molecules from simple aryl dihalides.Mechanistic studies indicate that an(alkoxycarbonyl)Ni(I)species might be generated via oxidation of Ni(0)species with an alkoxycarbonyl radical intermediate.Selective alkoxycarbonyl radical coupling over decarboxylative alkyl radical coupling is achieved here.展开更多
The medium-bandgap polymerized small molecule acceptors(PSMAs)have broad application scenarios.However,the effort in the molecular design of the high-performance medium-bandgap PSMAs is limited.In this article,we intr...The medium-bandgap polymerized small molecule acceptors(PSMAs)have broad application scenarios.However,the effort in the molecular design of the high-performance medium-bandgap PSMAs is limited.In this article,we introduce alkoxy groups as outer side chains and as substituents of the thiopheneπ-bridges of the high-performance PSMA PY-IT to synthesize a mediumbandgap PSMA PO-TO.Due to the fact that the non-covalent interaction between the alkoxy groups and the terminal groups of the small molecule acceptor(SMA)unit can weaken the intramolecular charge transfer(ICT)effect,the bandgap of PO-TO is enlarged and its absorption is blue-shifted compared with PY-IT,while the absorbance of PO-TO solution and film is enhanced significantly compared with that of PY-IT.When blended PO-TO with the polymer donor PBQx-TF,the corresponding all-polymer solar cells(all-PSCs)exhibit an open-circuit voltage(V_(oc))exceeding 1.04 V with a power conversion efficiency(PCE)of 13.75%.Furthermore,PO-TO was used as the third component to fabricate ternary all-PSCs with PBQx-TF as the polymer donor and PY-IT as the main polymer acceptor,and the ternary all-PSCs based on PBQx-TF:PY-IT:PO-TO(1:1:0.2,w/w/w)demonstrated a high PCE of 17.71%with simultaneously improved V_(oc)of 0.940 V,short-circuit current density(J_(sc))of 24.60 m A cm^(-2)and fill factor(FF)of76.81%.In comparison,the binary all-PSCs based on PBQx-TF:PY-IT showed a PCE of 16.77%.This result indicates that introducing alkoxy groups is a promising strategy for synthesizing high-performance medium-bandgap PSMAs.展开更多
Ultra-narrow bandgap(ultra-NBG)small molecule acceptors(SMAs)show great potential in organic solar cells(OSCs)due to the extended near-infrared(NIR)absorption.In this work,a synergetic alkoxy side-chain and chlorine-c...Ultra-narrow bandgap(ultra-NBG)small molecule acceptors(SMAs)show great potential in organic solar cells(OSCs)due to the extended near-infrared(NIR)absorption.In this work,a synergetic alkoxy side-chain and chlorine-contained end group strategy is employed to achieve A-DA'D-A type ultra-NBG SMAs by introducing alkoxy chains with oxygen atom at the second position into the thiopheneβposition as well as replacing the F atoms with Cl atoms in the end group.As a result,the heptacyclic BZO-4F shows a redshifted absorption onset(960 nm)compared with Y11(932 nm)without oxygen atoms in the side chains.Then,the fluorinated end groups are substituted with the chlorinated ones to synthesize BZO-4Cl.The absorption onset of BZO-4Cl is further redshifted to 990 nm,corresponding to an optical ultra-NBG of 1.25 eV.When blending with the polymer donor PBDB-T,the binary devices based on PBDB-T:BZO-4F and PBDB-T:BZO-4Cl deliver power conversion efficiencies(PCEs)over 12%.Furthermore,ternary devices with the addition of BZ4F-O-1 into PBDB-T:BZO-4Cl system achieve the optimal PCE of 15.51%.This work proposes a synergetic alkoxy side-chain and chlorine-contained end group strategy to achieve A-DA'D-A type ultra-NBG SMAs,which is important for future molecular design.展开更多
A series of poly(fluoroalkoxy thiophenes) have been prepared by electrochemical and chemical polymerization respectively. The substitution of thiophene by polyfluorinated alkoxy chains affords more favorable structure...A series of poly(fluoroalkoxy thiophenes) have been prepared by electrochemical and chemical polymerization respectively. The substitution of thiophene by polyfluorinated alkoxy chains affords more favorable structures in electronic effect and higher stabilities of their polymers than conventional alkoxy chain substituted polymers.展开更多
As a biomedical hydrogel, poly(β-hydroxyethyl methacrylate)has been widely studied and discussed, but studies on the synthesis and polymerization of those acrylates which contain both hydrophilic hydroxy group and al...As a biomedical hydrogel, poly(β-hydroxyethyl methacrylate)has been widely studied and discussed, but studies on the synthesis and polymerization of those acrylates which contain both hydrophilic hydroxy group and alkoxy group in the same ester group have received comparatively less attention. However Mikhailov first reported the synthesis of some γ-alkoxy-β-hydroxypropyl methacrylates and γ-aryloxy β-hydroxypropyl methacrylates from methacrylic acid and γ-alkoxy propylene or γ-展开更多
The cleavage of the alkoxy(Ar-O-R) ether bond present in anisole is an interesting hydrodeoxygenation(HDO) reaction, since this asymmetric group contains two different C–O bonds, Caryl–O or Calkyl–O, which could po...The cleavage of the alkoxy(Ar-O-R) ether bond present in anisole is an interesting hydrodeoxygenation(HDO) reaction, since this asymmetric group contains two different C–O bonds, Caryl–O or Calkyl–O, which could potentially cleave. Recent work on the HDO of anisole over Pt, Ru, and Fe catalysts has shown that a common phenoxy surface intermediate is formed on all three metals. The subsequent reaction path of this intermediate varies from metal to metal, depending on the metal oxophilicity. Over the less oxophilic Pt, phenol is the only primary product. By contrast, on the more oxophilic Fe catalyst, the sole primary product is benzene instead of phenol. On Ru, with intermediate oxophilicity, both benzene and phenol are primary products. In this contribution, we have investigated Rh catalysts of varying surface nanostructures. A combination of experimental measurements and computational calculations was used to explore the effects of varying metal coordination number, an additional parameter that can be used to control the oxophilicity of a metal. The results confirm that metal oxophilicity is a good descriptor for HDO performance of metal catalysts and it can be controlled via selection of metal type and/or metal extent of coordination. Small Rh metal clusters with low coordination metal sites are more active for the deoxygenation pathway but also quickly deactivated while large clusters with high coordination sites are more active toward hydrogenation and more stable.展开更多
The design and synthesis of new calamitic benzothiazole-based liquid crystals,2-[4-（4-alkyloxybenzoyloxy）-phenyl]ben-zothiazoles are presented.The target compound was characterized using spectroscopic techniques,suc...The design and synthesis of new calamitic benzothiazole-based liquid crystals,2-[4-（4-alkyloxybenzoyloxy）-phenyl]ben-zothiazoles are presented.The target compound was characterized using spectroscopic techniques,such as FT-IR,NMR（~1H and ^（13）C）,microanalysis and EI-MS.The liquid crystalline behaviours of these compounds were thoroughly examined by differential scanning calorimetry and polarizing optical microscope techniques.These materials exhibited enantiotropic nematic phase with high thermal stability（168℃）.Smectic A phase starts to emerge as monotropic（metastable） phase from C10 member and changes into enantiotropic（stable） phase from C12 and persists up to C16 members.展开更多
In this article,three novel and simple molecular structure with donor-acceptor(D-A) type copolymers via only head-to-head alkoxy(OR) and/or alkylthio(SR) side chains onto the bithiophene(BT) as donor units and fluorin...In this article,three novel and simple molecular structure with donor-acceptor(D-A) type copolymers via only head-to-head alkoxy(OR) and/or alkylthio(SR) side chains onto the bithiophene(BT) as donor units and fluorinated benzotriazole(FBTA) as acceptor unit,namely,PBTOR-FBTA,PBTOSR-FBTA and PBTSRFBTA,were successfully designed and synthesized.The impacts of sulfur-oxygen(S…O) or sulfur-sulfur(S-S) noncovalent interactions on their physicochemical properties,molecular stacking,carrier mobility,morphologies of blend films,as well as their photovoltaic performance were deeply and systematically studied.The introduction of SR side-chains suddenly lowered the highest occupied molecular orbital(HOMO) energy levels,blue-shifted absorption,enhanced π-π stacking,as well as improved morphology of the photoactive layer blends in comparison with the re ference polymer without SR side-chain.Polymer solar cells(PSCs) were fabricated to estimate their photovoltaic performance of the polymers.Under an optimized blend ratio of PBTSR-FBTA:PC71BM(1:0.8,w/w),the PBTSR-FBTAbased device exhibits a higher power conversion efficiency(PCE) of 6.25%,which is about 3.34 and 1.87 folds than that of the PBTOR-FBTA and PBTOSR-FBTA-based devices,respectively.Our research results demonstrate that the modification of the simple and low-cost SR side chains is an effective strategy to improve the photovoltaic performance of the polymers.展开更多
Organic scintillators have recently gained considerable attentions in X-ray detection for their potential applications in biomedical radiograph and security inspection.However,the weak X-ray absorption and/or ineffici...Organic scintillators have recently gained considerable attentions in X-ray detection for their potential applications in biomedical radiograph and security inspection.However,the weak X-ray absorption and/or inefficient exciton utilization have limited the development and commercialization of organic scintillators.Currently,high-performance X-ray organic scintillators are scarce and organic scintillators with dual triplet-harvesting channels have not been explored before.Here,we develop several proof-of-concept sulfone-based organic molecules,C1–C7,using different alkoxy chains to manipulate molecular packing mode.These materials exhibit dual triplet-harvesting channels of thermally activated delayedfluorescence(TADF)and room-temperature phosphorescence(RTP)in aggregated state.Inspiringly,these molecules display distinct radioluminescence under the X-ray stimulation.Among them,C6 behaves the highest light yield of 16,558 photons MeV-1.Moreover,clear X-ray images are demonstrated in both aggregated state and single-molecule level.High spatial resolutions of 15.0 and 10.6 line pairs per millimeter(lp mm-1)are achieved for rigid andflexible scintillator screens,exceeding most reported organic and conventional inorganic scintillators.These results highlight the great potential of organic molecules with TADF and RTP nature for efficient X-ray scintillation and imaging.展开更多
A regioselective C-C bond cleavage/aminocarbonylation cascade is presented. In recent years, tremendous progress has been made in the alkoxyl radical-mediated C-C bond cleavage of unstrained monocarbocycles. In contra...A regioselective C-C bond cleavage/aminocarbonylation cascade is presented. In recent years, tremendous progress has been made in the alkoxyl radical-mediated C-C bond cleavage of unstrained monocarbocycles. In contrast, the deconstruction and functionalization of bicyclic skeletons has been less developed and has mainly focused on the ring expansion process. Inspired by the aromatization-driven C-C bond cleavage, here we demonstrate a ring-opening/aminocarbonylation cascade under copper catalysis, in which the formation of a stable γ-lactam or succinimide skeleton reverses the selectivity of C-C cleavage. Remarkably, the photo and thermal assistance is not required when the succinimide skeleton is formed during the ring opening process. DFT calculations revealed that this unexpected ring-opening process is thermodynamically and kinetically favourable.展开更多
Main observation and conclusion Alkoxy radical-mediated carbon-carbon bond cleavages have emerged as a powerful strategy to complement traditional ionic-type transformations.However,carbon-carbon cleavage reaction tri...Main observation and conclusion Alkoxy radical-mediated carbon-carbon bond cleavages have emerged as a powerful strategy to complement traditional ionic-type transformations.However,carbon-carbon cleavage reaction triggered by alkoxy radical intermediate derived from the combination of alkyl radical and dioxygen,is scarce and underdeveloped.Herein,we report alkoxy radical,which was generated from alkyl radical and dioxygen,mediated selective cleavage of unstrained carbon-carbon bond for the oxysulfonylation of 1,1-disubstituted alkenes,providing facile access to a variety of valuableβ-keto sulfones.Mechanistic experiments indicated alkoxy radical intermediate that underwent subsequent regioselectiveβ-scission might be involved in the reaction and preliminary computational studies were conducted to provide a detailed explanation on the regioselectivity of the C-C bond cleavage.Notably,the strategy was successfully applied for constructing uneasily obtained architecturally intriguing molecules.展开更多
基金Project(2003B10506) supported by Science and Technology Department of Guangdong Province, China
文摘Acrylate latex modified by vinyl triisopropoxy silane (C-1706) was synthesized by seeded emulsion polymerization with anionic emulsifier sodium dodecyl sulphonate(SDS) and nonionic emulsifier OP-10 as the multiple emulsifiers at (78±2) ℃. The effects of different factors, such as the emulsifier, C-1706 monomer and its feeding manner on the properties of acrylate latex modified by C-1706 were investigated. The particle size distribution and the structure, the configuration, the weather durability and stain resistance of copolymer latex were characterized by particle size analyzer, Fourier transform infrared spectroscopy (FT-IR), transmission electron microscope(TEM), scanning electron microscope(SEM) and ultraviolet aging instrument respectively. The results show that SDS to OP-10 as multiple emulsifiers can lead to coordinated efficiency, the optimal emulsifier dosage is 2.4%?3.2%(mass fraction), and the mass ratio of SDS to OP-10 is 1?1? 1?2. The seeded emulsion polymerization can effectively introduce a organic-siloxane bonding in a macromolecule inter polymer, and the obtained acrylate latex modified by organic-siloxane possesses narrow distribution of particle size with mean diameter of 51.8?76.6 nm and has the excellent properties in weather durability and stain-resistance especially.
基金the financial support from the Science and Technology Development Plan Project of Jilin Province (No.20180520003JH)the Natural Science Fund Project of Changchun University of Science and Technology (No.XQNJJ2017-14)the Youth Innovation Promotion Association of Chinese Academy of Sciences (No.2015180)。
文摘Two n-butoxy-encapsulated dendritic thermally activated delayed fluorescent(TADF) emitters(namely O-D1 and O-D2) with the first-/second-generation carbazoledendrons are designed and synthesized via C—N coupling between carbazoledendrons and 2,4,6-tris(4-bromophenyl)-1,3,5-triazine core.It is found that,compa red with the commo nly-used tert-butyl groups,the use of n-butoxy encapsulation groups can lead to smallersinglet-triplet energy gap for the dendrimers,producing stronger TADF effect together with faster reverse intersystem crossing process.Solution-processed TADF organic light-emitting diodes(OLEDs) utilizingalkoxy-encapsulated dendrimers O-D1 and O-D2 as emitters exhibitstate-of-the-art device efficiency withthe maximum external quantum efficiency up to 16.8% and 20.6%,respectively,which are ~1.6 and~2.0 times that of the tert-butyl-encapsulated counterparts.These results suggest that alkoxy encapsulation of the carbazole-based TADF dendrimers can be a promising approach for developing highly efficient emitters for solution-processed OLEDs.
基金the Science & Technology Office and Development &Innovation Committee of Guangzhou Province(No.2003B 10506)
文摘An acrylate emulsion was modified by adding vinyltriisopropoxy silane （trade name C-1706）. By adding the multiple emulsifier which consists of an anionic emulsifier, sodium dodecyl benzene sulfonate （SDBS） and nonionic emulsifier, octyl phenolic divinyl oxide （OP-10）, the acrylosilane microemulsion was synthesized by seeded emulsion polymerization. The influential factors including the kind and the adding amount of emulsifiers and the monomer variety of alkoxy silane and the added methods which influence on the properties of the microemulsion were investigated. It is found that SDBS and OP-10 as multiple emulsifiers with mass ratio of 1：1 and the adding amount of 2.5%-3.5% can act on co-effect for emulsion polymerization. The C-1706 possesses bulky isopropoxy substituent that can reduce hydrolysis reactivity during the polymerization process, so as to not only make the process smoothly but also advance the store stability of the emulsion. Moreover, the latter-addition mode of C-1706 can restrain its hydrolysis activity and polycondensation reaction during the polymerization process of the emulsion. The structure, the film cross section, the particle size and its distribution of the microemulsion were analyzed by the Fourier Transform Infrared Ray Spectrum （FTIR）, Scanning Electron Microscopy （SEM） and a particle size analyzer, respectively. The results show that the particle diameter of the modified microemulsion can be controlled between 50 and 70 nm and its film hardness is 7.3. Only adding 1.5% of C-1706 into the system of emulsion polymerization can apparently improve the weathering resistance of the microemulsion, which undergo degradation with chromatism（△E） is 1.6 after 3 600 hours of QUV-aging.
基金The project is supported by Natural Science Foundation of Shandong.
文摘In this paper, we report an improved method for preparing 2--alkoxy 5 fluoro--3H --4--pyrimidone from 2--chloro--5--fluoro--3H--4--pyrimidone and sodium alkoxide under normal pressure at reflux temperature. Some new compounds were synthesized in higher yield by this method.
文摘The rearrangement of α-substituted phenyl-α, α′-dimethoxypropanones (R1) was recently proved to he an [1, 3] siqmatropic migration of methoxy group by study of LFER, solvent effect, crossover experiment, and by other means. The rearrangement catalysed by trace of totuenesulfonic acid gave a negligible value of the Hammett reaction constant. Further experimental results show that the electronic effect of substituent on the aromatic ring for the rearrangement in neutral medium is much greater (Table 1). We propose sigmatropic migration
基金supported by the National Natural Science Foundation of China(Nos.22101237 and 22171233)Collaborative Fund of Luzhou Government and Southwest Medical University(Nos.2023LZXNYDJ019 and 2024LZXNYDJ050)+1 种基金the Science and Technology Program of Luzhou City(No.2024RCX207)the research fund of Southwest Medical University(Nos.2023QN091 and 2022QN057).
文摘N,O-Spiroaminals have potential biological activities and abilities to modulate the physicochemical and pharmacokinetic properties of drug molecules.However,effective catalytic methods for the efficient construction of N,O-spiroaminals are still limited to date.Herein,we report a novel 1,1,2-trifunctionalization of unactivated alkenes to rapidly and efficiently obtain a diverse array of architecturally intriguing N,O-spiroaminals.This methodology exhibits broad substrate scope,good functional group compatibility,and potential synthetic utility by a scale-up reaction,diverse product derivatizations and late-stage functionalization of complex biorelevant molecule.Notably,this transformation selectively allows for the formation of three new chemical bonds(C–O,C–C,and C–N)and one spiro quaternary carbon center across C-C double bonds.
基金financial support from the Marine S&T Fund of Shandong Province for Pilot National Laboratory for Marine Science and Technology(Qingdao)(No.2022QNLM030003-2)the National Natural Science Foundation of China(No.21977088)the National Natural Science Foundation of China-Shandong Joint Fund(No.U1906213)。
文摘Ag_(2)CO_(3)-promoted dehydroxymethylative fluorination of aliphatic alcohols has been achieved with Selectfluor as both oxidant and fluorine source.The reaction involvesβ-fragmentation of primary alkoxy radicals,followed by the fluorination of the resulting C-centered radical intermediates.The transformation proceeds under mild reaction conditions and exhibits a broad substrate scope,thus opening up a new entrance to the synthesis of fluorinated constructs includingα-fluoroimides and 1-fluoroalkyl benzoates as well as secondary and tertiary alkyl fluorides like versatile 2-fluoro-2-alkyl 1,3-propandiol derivatives.The divergent functionalization of the obtainedα-fluoroimides enables an efficient access to amine derivatives through C-F bond activation under the action of BF_(3)·OEt_(2).
基金the financial support from the NSFC of China(21772208 and 21633013)Natural Science Foundation of Jiangsu Province(BK20201183)the Key Research Program of Frontier Sciences of Chinese Academy of Sciences(QYZDJSSW-SLH051).
文摘A new approach for radical cross coupling of organic halides and oxalates toward esters has been developed via photoredox nickel dual catalysis.This method has been demonstrated for transformation of a wide range of aryl,heteroaryl,alkenyl,and alkyl bromides to various esters under mild conditions.Notably,fluoro-,chloro-,or iodo-substituents on the aryl bromides remain after the coupling reaction,which has been applied for the easy synthesis of drug molecules from simple aryl dihalides.Mechanistic studies indicate that an(alkoxycarbonyl)Ni(I)species might be generated via oxidation of Ni(0)species with an alkoxycarbonyl radical intermediate.Selective alkoxycarbonyl radical coupling over decarboxylative alkyl radical coupling is achieved here.
基金supported by the National Key Research and Development Program of China(2019YFA0705900)the Ministry of Science and Technology,the National Natural Science Foundation of China(51820105003,21734008,52203248,61904181,52173188)+1 种基金the Key Research Program of the Chinese Academy of Sciences(XDPB13)the Basic and Applied Basic Research Major Program of Guangdong Province(2019B030302007)。
文摘The medium-bandgap polymerized small molecule acceptors(PSMAs)have broad application scenarios.However,the effort in the molecular design of the high-performance medium-bandgap PSMAs is limited.In this article,we introduce alkoxy groups as outer side chains and as substituents of the thiopheneπ-bridges of the high-performance PSMA PY-IT to synthesize a mediumbandgap PSMA PO-TO.Due to the fact that the non-covalent interaction between the alkoxy groups and the terminal groups of the small molecule acceptor(SMA)unit can weaken the intramolecular charge transfer(ICT)effect,the bandgap of PO-TO is enlarged and its absorption is blue-shifted compared with PY-IT,while the absorbance of PO-TO solution and film is enhanced significantly compared with that of PY-IT.When blended PO-TO with the polymer donor PBQx-TF,the corresponding all-polymer solar cells(all-PSCs)exhibit an open-circuit voltage(V_(oc))exceeding 1.04 V with a power conversion efficiency(PCE)of 13.75%.Furthermore,PO-TO was used as the third component to fabricate ternary all-PSCs with PBQx-TF as the polymer donor and PY-IT as the main polymer acceptor,and the ternary all-PSCs based on PBQx-TF:PY-IT:PO-TO(1:1:0.2,w/w/w)demonstrated a high PCE of 17.71%with simultaneously improved V_(oc)of 0.940 V,short-circuit current density(J_(sc))of 24.60 m A cm^(-2)and fill factor(FF)of76.81%.In comparison,the binary all-PSCs based on PBQx-TF:PY-IT showed a PCE of 16.77%.This result indicates that introducing alkoxy groups is a promising strategy for synthesizing high-performance medium-bandgap PSMAs.
基金This work was supported by the National Natural Science Foundation of China(Nos.52125306,22005347).
文摘Ultra-narrow bandgap(ultra-NBG)small molecule acceptors(SMAs)show great potential in organic solar cells(OSCs)due to the extended near-infrared(NIR)absorption.In this work,a synergetic alkoxy side-chain and chlorine-contained end group strategy is employed to achieve A-DA'D-A type ultra-NBG SMAs by introducing alkoxy chains with oxygen atom at the second position into the thiopheneβposition as well as replacing the F atoms with Cl atoms in the end group.As a result,the heptacyclic BZO-4F shows a redshifted absorption onset(960 nm)compared with Y11(932 nm)without oxygen atoms in the side chains.Then,the fluorinated end groups are substituted with the chlorinated ones to synthesize BZO-4Cl.The absorption onset of BZO-4Cl is further redshifted to 990 nm,corresponding to an optical ultra-NBG of 1.25 eV.When blending with the polymer donor PBDB-T,the binary devices based on PBDB-T:BZO-4F and PBDB-T:BZO-4Cl deliver power conversion efficiencies(PCEs)over 12%.Furthermore,ternary devices with the addition of BZ4F-O-1 into PBDB-T:BZO-4Cl system achieve the optimal PCE of 15.51%.This work proposes a synergetic alkoxy side-chain and chlorine-contained end group strategy to achieve A-DA'D-A type ultra-NBG SMAs,which is important for future molecular design.
基金supported by the National Natural Science Foundation of China.
文摘A series of poly(fluoroalkoxy thiophenes) have been prepared by electrochemical and chemical polymerization respectively. The substitution of thiophene by polyfluorinated alkoxy chains affords more favorable structures in electronic effect and higher stabilities of their polymers than conventional alkoxy chain substituted polymers.
文摘As a biomedical hydrogel, poly(β-hydroxyethyl methacrylate)has been widely studied and discussed, but studies on the synthesis and polymerization of those acrylates which contain both hydrophilic hydroxy group and alkoxy group in the same ester group have received comparatively less attention. However Mikhailov first reported the synthesis of some γ-alkoxy-β-hydroxypropyl methacrylates and γ-aryloxy β-hydroxypropyl methacrylates from methacrylic acid and γ-alkoxy propylene or γ-
基金supported by the U.S.Department of Energy,DOE/EPSCOR(Grant DESC0004600)
文摘The cleavage of the alkoxy(Ar-O-R) ether bond present in anisole is an interesting hydrodeoxygenation(HDO) reaction, since this asymmetric group contains two different C–O bonds, Caryl–O or Calkyl–O, which could potentially cleave. Recent work on the HDO of anisole over Pt, Ru, and Fe catalysts has shown that a common phenoxy surface intermediate is formed on all three metals. The subsequent reaction path of this intermediate varies from metal to metal, depending on the metal oxophilicity. Over the less oxophilic Pt, phenol is the only primary product. By contrast, on the more oxophilic Fe catalyst, the sole primary product is benzene instead of phenol. On Ru, with intermediate oxophilicity, both benzene and phenol are primary products. In this contribution, we have investigated Rh catalysts of varying surface nanostructures. A combination of experimental measurements and computational calculations was used to explore the effects of varying metal coordination number, an additional parameter that can be used to control the oxophilicity of a metal. The results confirm that metal oxophilicity is a good descriptor for HDO performance of metal catalysts and it can be controlled via selection of metal type and/or metal extent of coordination. Small Rh metal clusters with low coordination metal sites are more active for the deoxygenation pathway but also quickly deactivated while large clusters with high coordination sites are more active toward hydrogenation and more stable.
基金Universiti Tunku Abdul Rahman(UTAR) for the UTAR Research Fund (No.6200/H02)the Malaysia Toray Science Foundation(No.4359/000) for funding this project
文摘The design and synthesis of new calamitic benzothiazole-based liquid crystals,2-[4-（4-alkyloxybenzoyloxy）-phenyl]ben-zothiazoles are presented.The target compound was characterized using spectroscopic techniques,such as FT-IR,NMR（~1H and ^（13）C）,microanalysis and EI-MS.The liquid crystalline behaviours of these compounds were thoroughly examined by differential scanning calorimetry and polarizing optical microscope techniques.These materials exhibited enantiotropic nematic phase with high thermal stability（168℃）.Smectic A phase starts to emerge as monotropic（metastable） phase from C10 member and changes into enantiotropic（stable） phase from C12 and persists up to C16 members.
基金financially supported by grants from the National Natural Science Foundation of China(Nos.51573154,51673031)The Natural Science Foundation of Jiangsu Higher Institutions of China(No.18KJA480001)+2 种基金the Youth Science and Technology Foundation of Sichuan Province(No.2013JQ0032)the key Laboratory of Environment-Friendly Chemistry and Applications of Ministry of Education(No.2018HJYH01)the Natural Science Foundation of Jiangsu Province(No.BK20141151)。
文摘In this article,three novel and simple molecular structure with donor-acceptor(D-A) type copolymers via only head-to-head alkoxy(OR) and/or alkylthio(SR) side chains onto the bithiophene(BT) as donor units and fluorinated benzotriazole(FBTA) as acceptor unit,namely,PBTOR-FBTA,PBTOSR-FBTA and PBTSRFBTA,were successfully designed and synthesized.The impacts of sulfur-oxygen(S…O) or sulfur-sulfur(S-S) noncovalent interactions on their physicochemical properties,molecular stacking,carrier mobility,morphologies of blend films,as well as their photovoltaic performance were deeply and systematically studied.The introduction of SR side-chains suddenly lowered the highest occupied molecular orbital(HOMO) energy levels,blue-shifted absorption,enhanced π-π stacking,as well as improved morphology of the photoactive layer blends in comparison with the re ference polymer without SR side-chain.Polymer solar cells(PSCs) were fabricated to estimate their photovoltaic performance of the polymers.Under an optimized blend ratio of PBTSR-FBTA:PC71BM(1:0.8,w/w),the PBTSR-FBTAbased device exhibits a higher power conversion efficiency(PCE) of 6.25%,which is about 3.34 and 1.87 folds than that of the PBTOR-FBTA and PBTOSR-FBTA-based devices,respectively.Our research results demonstrate that the modification of the simple and low-cost SR side chains is an effective strategy to improve the photovoltaic performance of the polymers.
基金National Natural Science Foundation of China,Grant/Award Number:52022071Shenzhen Science and Technology Program,Grant/Award Number:ZDSYS20210623091813040。
文摘Organic scintillators have recently gained considerable attentions in X-ray detection for their potential applications in biomedical radiograph and security inspection.However,the weak X-ray absorption and/or inefficient exciton utilization have limited the development and commercialization of organic scintillators.Currently,high-performance X-ray organic scintillators are scarce and organic scintillators with dual triplet-harvesting channels have not been explored before.Here,we develop several proof-of-concept sulfone-based organic molecules,C1–C7,using different alkoxy chains to manipulate molecular packing mode.These materials exhibit dual triplet-harvesting channels of thermally activated delayedfluorescence(TADF)and room-temperature phosphorescence(RTP)in aggregated state.Inspiringly,these molecules display distinct radioluminescence under the X-ray stimulation.Among them,C6 behaves the highest light yield of 16,558 photons MeV-1.Moreover,clear X-ray images are demonstrated in both aggregated state and single-molecule level.High spatial resolutions of 15.0 and 10.6 line pairs per millimeter(lp mm-1)are achieved for rigid andflexible scintillator screens,exceeding most reported organic and conventional inorganic scintillators.These results highlight the great potential of organic molecules with TADF and RTP nature for efficient X-ray scintillation and imaging.
基金supported by the National Natural Science Foundation of China (Nos. 22171220)the Fundamental Research Funds of the Central Universities (No. xtr072022003)。
文摘A regioselective C-C bond cleavage/aminocarbonylation cascade is presented. In recent years, tremendous progress has been made in the alkoxyl radical-mediated C-C bond cleavage of unstrained monocarbocycles. In contrast, the deconstruction and functionalization of bicyclic skeletons has been less developed and has mainly focused on the ring expansion process. Inspired by the aromatization-driven C-C bond cleavage, here we demonstrate a ring-opening/aminocarbonylation cascade under copper catalysis, in which the formation of a stable γ-lactam or succinimide skeleton reverses the selectivity of C-C cleavage. Remarkably, the photo and thermal assistance is not required when the succinimide skeleton is formed during the ring opening process. DFT calculations revealed that this unexpected ring-opening process is thermodynamically and kinetically favourable.
基金Fund of Luzhou Government and Southwest Medical University(Nos.2019LZXNYDJ28,2018LZXNYD-ZK33,2018LZXNYD-ZK39)the Open Project of Central Nervous System Drug Key Laboratory of Sichuan Province(No.200023-01SZ)the research fund of Southwest Medical University(Nos.2017-ZRZD-020 and 2017-ZRQN-031).
文摘Main observation and conclusion Alkoxy radical-mediated carbon-carbon bond cleavages have emerged as a powerful strategy to complement traditional ionic-type transformations.However,carbon-carbon cleavage reaction triggered by alkoxy radical intermediate derived from the combination of alkyl radical and dioxygen,is scarce and underdeveloped.Herein,we report alkoxy radical,which was generated from alkyl radical and dioxygen,mediated selective cleavage of unstrained carbon-carbon bond for the oxysulfonylation of 1,1-disubstituted alkenes,providing facile access to a variety of valuableβ-keto sulfones.Mechanistic experiments indicated alkoxy radical intermediate that underwent subsequent regioselectiveβ-scission might be involved in the reaction and preliminary computational studies were conducted to provide a detailed explanation on the regioselectivity of the C-C bond cleavage.Notably,the strategy was successfully applied for constructing uneasily obtained architecturally intriguing molecules.
