Polymerizations of linear α-olefins(CnH2n, CH2=CH―R, R = Cn-2) catalyzed by early transition metals typically afford amorphous polymers with alkyl chains(Cn-2), while chain-straightening polymerizations of α-olefin...Polymerizations of linear α-olefins(CnH2n, CH2=CH―R, R = Cn-2) catalyzed by early transition metals typically afford amorphous polymers with alkyl chains(Cn-2), while chain-straightening polymerizations of α-olefins with nickel-based catalysts produce semicrystalline polyolefins. Polymerizations of various α-olefins were carried out using an α-diamine nickel catalyst with a significantly distorted chelating ring. The influences of temperature, monomer concentration, and chain length of α-olefins on polyolefin microstructure were examined in detail. The α-diamine nickel catalyst realized highly regioselective 2,1-insertion of α-olefins regardless of reaction temperature and monomer concentration. Increased chain length of α-olefins led to the formation of more linear polyolefin.Semicrystalline polyolefins with high melting temperatures(Tm) were made from α-olefins through highly regioselective 2,1-insertion and precise chain-straightening.展开更多
A series of pyrazolylimine ligated Co(II) and Fe(II) complexes with general formula of(PhC=N(C_6H_3(R_1)2-2,6)(C_3 HN_2(R_2)2-3,5)MtCl_2(R_1 = Me, R_2 = H, Mt = Co(1 a), Fe(2 a); R_1 = Me, R_2 = Me, Mt = Co(1b), Fe(2b...A series of pyrazolylimine ligated Co(II) and Fe(II) complexes with general formula of(PhC=N(C_6H_3(R_1)2-2,6)(C_3 HN_2(R_2)2-3,5)MtCl_2(R_1 = Me, R_2 = H, Mt = Co(1 a), Fe(2 a); R_1 = Me, R_2 = Me, Mt = Co(1b), Fe(2b); R_1 = iPr, R_2 = H, Mt = Co(1 c), Fe(2 c); R_1 = i Pr, R_2 = Me, Mt = Co(1 d), Fe(2 d); R_1 = i Pr, R_2 = Ph, Mt = Co(1 e), Fe(2 e)) were synthesized and thoroughly characterized.Determined by single crystal X-ray diffraction, complexes 1 b and 2 b revealed dimeric structures, in which distorted trigonal bipyramid geometries were adopted for each metal centers. In the presence of ethylaluminum sesquichloride(EASC), all the cobalt complexes displayed high activities in 1,3-butadiene polymerization, affording polybutadienes with predominant cis-1,4 contents(up to 97.0%).Influences of ligand structure and polymerization parameters on catalytic performance were investigated systematically. For pyrazolylimine iron(II) dichloride complexes, the catalytic activities and microstructures of the resultant polybutadienes were highly dependent on ligand structures and polymerization conditions. For complex 2 a, changing cocatalyst from trialkyl aluminums to methyl aluminoxane(MAO) led to an shift of selectivity from high cis-1,4-to trans-1,4-/1,2-manner. Being activated by MAO, complexes 2 a and 2 b gave trans-1,4-/1,2-binary polybutadienes, while complexes 2 c, 2 d, and 2 e afforded cis-1,4-enriched polymers.展开更多
Through neodymium-mediated coordinative chain transfer copolymerizaiton(CCTcoP),polyisoprenes bearing dual hydroxylated mini-blocky chain-ends were prepared via a three-step strategy.Kinetic studies revealed that,the ...Through neodymium-mediated coordinative chain transfer copolymerizaiton(CCTcoP),polyisoprenes bearing dual hydroxylated mini-blocky chain-ends were prepared via a three-step strategy.Kinetic studies revealed that,the polymerization demonstrated typical features of CCTcoP across the whole polymerization process,i.e.,quasi-living polymerization characteristic,tunable molecular weights,narrow molecular weight distributions,and atom economies.Comparing to previously reported CCTP homopolymerization systems,the presence of oxygen-containing IpOAl polar comonomer slowed down chain transfer rates obviously,rendering slightly higher molecular weights of the resultant PIps and smaller Np(number of polymer chains per Nd atom)values.Moreover,to mimic the structure of natural rubber,the hydroxyl end groups can be facilely modified into phosphonate,amide,and UPy,whose structures were further confirmed by NMR spectra.Incorporation these functionalities could greatly improve the hydrophilic properties of the polymers,as revealed from the significantly reduced static water contact angles.展开更多
Mechanistic transformation approach has been widely applied in polymer synthesis due to its unique feature combining structurally different polymers prepared by different polymerization mechanisms.Reported methods for...Mechanistic transformation approach has been widely applied in polymer synthesis due to its unique feature combining structurally different polymers prepared by different polymerization mechanisms.Reported methods for the formation of block and graft copolymers through mechanistic transformation involve almost all polymerizations modes.However,certain polymerization processes require extensive purification processes,which can be time-consuming and problematic.Recent developments on controlled/living polymerizations involving radical and cationic mechanisms with the ability to control molecular weight and functionality led to new pathways for mechanistic transformations.In this mini-review,we systematically discussed relevant advances in the field through three main titles namely(i)from radical to cationic mechanism,(ii)from cationic to radical mechanism,and(iii)application of specific catalyst systems for both radical and cationic polymerizations.展开更多
We report herein the cationic polymerization of isobutylene(IB)under mild conditions is realized with a new binary initiation system generated by simply mixing a Lewis super acid Al(C_(6)F_(5))_(3) and a substituted p...We report herein the cationic polymerization of isobutylene(IB)under mild conditions is realized with a new binary initiation system generated by simply mixing a Lewis super acid Al(C_(6)F_(5))_(3) and a substituted phenol(RPhOH).Polymers with medium and/or high molecular weights(M_(W)=4.9×10^(4)-27.7×10^(4) g·mol^(-1))can be obtained in toluene and temperatures from-20℃to 0℃.NMR spectrum analysis and DFT sim ulation reveals the in situ generated acidic coordinating complex Ak(C_(6)F_(5))_(3)·RPhOH is the initiating active species,which fu rther tran sformed into the ion-pair[Al(C_(6)F_(5))_(3)ORPh]^(-)[PIB]^(+)of the active intermediates upon growing IB monomers where the counter anion[Al(C_(6)F_(5))_(3)R^(O)Ph]-coordinates to the macrocation via the phenoxy oxygen.The catalyst performances are the concert effects of the steric bulkiness and electronics of the counter anion on the coordinating strength to the macrocation,which is significant to the stability of the active species.展开更多
Multicomponent polymerizations(MCPs)are powerful tools to synthesize functional polymers with great structural diversity,low cost and high efficiency,which usually generate single polymer product.Herein,a robust one-p...Multicomponent polymerizations(MCPs)are powerful tools to synthesize functional polymers with great structural diversity,low cost and high efficiency,which usually generate single polymer product.Herein,a robust one-pot diamines,CS_(2)and monoisocyanide-participated catalyst-free polymerization was developed at room temperature to produce polythiourea and thioformamide simultaneously in equal equivalent,which was featured with cheap monomers,simple operation and mild condition,affording various polythioureas with high Mws of up to 4.75×10^(4)g/mol in high yields of up to 98%.Polythioureas with varied chain composition and sequence-controlled structure could be synthesized in 62 g-scale from copolymerization or multicomponent tandem polymerization,enabling facile tuning of thermal property,crystallinity,mechanical property,and fluorescence.The abundant irregular hydrogen bonds endowed the polythioureas excellent glassy state self-healing property at room temperature or below 0℃.This polymerization provided an efficient and economic approach to access functional polythioureas.展开更多
The alternating copolymerization of hydroxyalkyl vinyl ethers and dialkyl maleates is investigated by conventional radical polymerization and reversible addition-fragmentation chain transfer polymerization(RAFT).The i...The alternating copolymerization of hydroxyalkyl vinyl ethers and dialkyl maleates is investigated by conventional radical polymerization and reversible addition-fragmentation chain transfer polymerization(RAFT).The influence of comonomer structure,comonomer feeding ratios,and monomer concentrations on the copolymerization and the copolymer structure have been investigated systematically.With 2-hydroxyethyl vinyl ether(HEVE)and dimethyl maleates(DMM)as comonomers,a well-defined alternating copolymer is prepared with M_(n)=3400 and M_(w)/M_(n)=1.93 up to 71.6% monomer.The alternating sequential chain structure of the copolymers has been proved by both NMR and matrixassisted laser desorption/ionization time-of-flight mass spectrometry(MALDI-TOF MS).The experimental reactivity ratios and theoretical calculated highest occupied molecular orbital and the lowest unoccupied molecular orbital of vinyl ethers and alkyl maleates support that these monomer pairs have tendency to form alternating copolymers.With 2-cyanopropan-2-yl N-methyl-N-(pyridin-4-yl)carbamodithioate as the RAFT agent,the molecular weight of HEVE and DMM copolymer increases with the monomer conversion,demonstrating a controlled radical polymerization feature with well-controlled molecular weight and relatively narrower molecular weight distribution.With alternating copolymer of HEVE and DMM as macro-CTA(M_(n)=5200 and M_(w)/M_(n)=1.46),both the chain extension with HEVE and DMM(M_(n)=10400 and M_(w)/M_(n)=1.72)and block copolymerization with vinyl acetate have been successfully achieved(M_(n)=8500 and M_(w)/M_(n)=1.52).展开更多
Branched polyolefins with controllable topology structures were generated from the chain-walking(co)polymerizations of ethylene,1-pentene(1P)and 2-pentene(2P)using Brookhart-typeα-diimine Ni(II)-based catalysts posse...Branched polyolefins with controllable topology structures were generated from the chain-walking(co)polymerizations of ethylene,1-pentene(1P)and 2-pentene(2P)using Brookhart-typeα-diimine Ni(II)-based catalysts possessing different para-substituted groups,{[(4-R-2-Et-6-Me-C6H2N=C)2Nap]NiBr2,Nap:1,8-naphthdiyl;R=CHMePh,Ni1;R=Ph,Ni2;R=H,Ni3}.The X-ray diffraction analysis demonstrated that the crystalline structure of Ni1′is in centrosymmetric dimer structure mode with the bimetallic Ni center connected by two bromide bridges.The para-sec-phenethyl moiety in the catalyst Ni1 obviously improved its catalytic performance and thermal stability in the ethylene polymerization.The Ni1/Et2AlCl system showed great catalytic activities(up to 7.73×106 g·mol-1·h-1)and achieved polyethylene(PE)with alkyl chains,including Me,Et,n-Pr,n-Bu,sec-Bu branches and longer chains(Lg).Compared with the 1-pentene polymerization,this catalyst system successfully mediated the polymerization of 2P to give highly branched polymers with approximately 195 branches/1000C possessing Me,Et,and n-Pr branches and a long methylene sequence due to the monomer isomerization.The Et branches derived from 2,3-insertion is slightly less than the sum of Me and n-Pr branches derived from 3,2-insertion,indicating that the 3,2-insertion mode is a slightly favorable pathway in the polymerization of 2P.展开更多
Polythioureas with great potential in precious metal recovery materials,dielectric materials,light refractive materials,self-healing materials,and adhesives have become a group of popular polymer materials.While vario...Polythioureas with great potential in precious metal recovery materials,dielectric materials,light refractive materials,self-healing materials,and adhesives have become a group of popular polymer materials.While various synthetic approaches have been reported for different polythiourea structures,which generally involve expensive and toxic monomers,several polythiourea structures,such as asymmetric aromatic polythioureas,still have limited access.Herein,a base-catalyzed multicomponent polymerization(MCP)of elemental sulfur,diisocyanides,and diamines was developed,which was generally applicable for both aromatic amines with low reactivity and aliphatic amines with high nucleophilicity,affording polythioureas with great structural diversity,high Mw s of up to 107,700 g/mol and high yields of up to 99%.Moreover,aromatic polythioureas with different aromatic spacers installed on each side of the thiourea moiety could be facilely synthesized.Amine exchange reactions were studied for thiourea compounds or polythioureas,indicating that the C-N bonds of the thiourea moiety on the aromatic substitute side were more labile compared with those on the aliphatic substitute side,rendering the potential controllable degradation of different polythiourea structures.The polythioureas generally possess high thermal stability,with the glass transition temperatures ranging from 121 to 169℃.These polythioureas could efficiently absorb Hg2+from polluted water,and aromatic polythioureas generally showed better performance compared with semi-aromatic and aliphatic polythioureas.This work has hence provided a general synthetic approach for various aliphatic,aromatic,and semi-aromatic polythioureas with symmetric or asymmetric thiourea structures.The dynamic covalent bond nature of thioureas endowed these polymer materials with controllable degradation,making them sustainable functional polymer materials.展开更多
The development of C-H activation-based polymerization strategies for the facile and efficient construction of novel functional fused heterocyclic polymers is an important but challenging task.Herein,we report a facil...The development of C-H activation-based polymerization strategies for the facile and efficient construction of novel functional fused heterocyclic polymers is an important but challenging task.Herein,we report a facile and atom-economical C-H activation/annulation polymerization(CAAP)approach that enables the in-situ formation of unique diheterocycle-fused polymers from readily available monomers based on the C-H activation of olefins.The rhodium-catalyzed polymerizations of fumaric acid and internal diynes proceed smoothly under mild conditions,producing a series of multisubstituted poly(dilactone)s with high molecular weights(M_(w)up to 109,600)in moderate to high yields of up to 98.4%.The presence of multiple aryl substituents around the dilactone units endows the resulting polymers with good solution processibility and readily tunable fluorescent properties.Most of the synthesized poly(dilactone)s exhibit aggregation-induced emission(AIE)properties,showing efficient aggregate-state fluorescence.The AIE-active poly(dilactone)can function as a good lysosome-specific fluorescent probe in biological imaging with low cytotoxicity.It is anticipated that these straightforward and economic CAAP reactions together with the structure-property relationship study in this work could promote the exploration of fused heterocyclic polymer materials with more diversified structures and advanced functionalities.展开更多
Water,characterized by its safety,abundance,low cost,and sustainability,has garnered increasing attention in polymer synthesis.It has been utilized as a solvent or a comonomer in polymerizations based on triple-bond b...Water,characterized by its safety,abundance,low cost,and sustainability,has garnered increasing attention in polymer synthesis.It has been utilized as a solvent or a comonomer in polymerizations based on triple-bond building blocks for the construction of functional polymers.Currently,distinct progress has been made;however,no such review was presented.This Review aims to summarize the progress in alkyne-based polymerizations in aqueous media with the“on-water”effect,water-involved alkyne-based polymerizations,and water-involved isocyanide-based polymerizations.The catalyst systems,reaction conditions,post-modification strategies,and the properties and applications of the resulting polymers are summarized.Furthermore,the challenges and opportunities in this field are briefly discussed.展开更多
Vinyl polymers are widely used in modern society,but their all-carbon backbones make them highly resistant to degradation.One of the most effective solutions is to copolymerize them with cleavable monomers,resulting i...Vinyl polymers are widely used in modern society,but their all-carbon backbones make them highly resistant to degradation.One of the most effective solutions is to copolymerize them with cleavable monomers,resulting in degradable polymers that maintain thermal and mechanical properties similar to those of the original materials.Thionolactones have emerged as promising comonomers;however,only a few thionolactones are currently available for the preparation of degradable vinyl-based copolymers with unique reactivity.In this study,we developed a seven-membered,benzene-fused thionolactone,MBDT,as a comonomer and synthesized degradable polystyrene and its derivatives with thioester groups distributed along the chain through both radical and cationic copolymerizations.These copolymers can be degraded into short-chain fragments,which can then be recovered through oxidative repolymerization.Additionally,leveraging MBDT’s high copolymerization reactivity with styrene,we successfully conducted reversible addition−fragmentation chain transfer(RAFT)copolymerization,achieving controlled molecular weights(M_(n)’s)and narrow dispersities(Đ<1.2).Furthermore,we also successfully prepared degradable poly(p-methoxystyrene)via the cationic copolymerization of MBDT and p-methoxystyrene(MOS).展开更多
Selenium-containing polymers with fascinating functionalities such as stimuli-responsive property,enzyme mimics,antioxidant activity,promotion of immune-cell activity,anticancer activity,and controlled delivery proper...Selenium-containing polymers with fascinating functionalities such as stimuli-responsive property,enzyme mimics,antioxidant activity,promotion of immune-cell activity,anticancer activity,and controlled delivery property,are highly desired,but rarely developed due to their underexplored synthetic methods.Herein,through careful design of monomeric structures and polymerization conditions,we report a series of catalyst-free multicomponent polymerizations(MCPs)of elemental selenium with aliphatic/aromatic diamines and diisocyanides that directly converted selenium to polyselenoureas with long-term stability,good solubility,well-characterized structures,and unique functionalities.The MCPs enjoyed broad monomer scope and fast conversion in 1 min,delivering 18 polyselenoureas with high molecular weights(M_(w)s up to 94,600 g/mol)in high yields(up to 99%).Furthermore,the polyselenoureas could be used for the extraction of Au^(3+)from mixed-metal ion solutions under practical conditions with high selectivity,sensitivity(<1μg/L),efficiency(>99.99%),and capacity(up to 665.60 mg·Au^(3+)/g)within 1 min.Further,the elemental gold was recoverable after the pyrolysis of the polymer complexes.展开更多
Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynam...Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynamic size and slower degradation.It is key to develop facile methods to large-scale synthesis of polymer rings with tunable compositions and microstructures.Recent progresses in large-scale synthesis of polymer rings against single-chain dynamic nanoparticles,and the example applications in synchronous enhancing toughness and strength of polymer nanocomposites are summarized.Once there is the breakthrough in rational design and effective large-scale synthesis of polymer rings and their functional derivatives,a family of cyclic functional hybrids would be available,thus providing a new paradigm in developing polymer science and engineering.展开更多
The ionothermal reaction between CuCl_(2),1,4-bis(1,2,4-triazol-1-ylmethyl)benzene(BBTZ),and(NH_(4))_(6)Mo_(7)O_(24) in 1-ethyl-3-methylimidazolium bromide((Emim)Br)led to a new octamolybdate-based coordination polyme...The ionothermal reaction between CuCl_(2),1,4-bis(1,2,4-triazol-1-ylmethyl)benzene(BBTZ),and(NH_(4))_(6)Mo_(7)O_(24) in 1-ethyl-3-methylimidazolium bromide((Emim)Br)led to a new octamolybdate-based coordination polymer(Emim)2[Cu(BBTZ)_(2)(β-Mo_(8)O_(26))](Mo_(8)-CP).Mo_(8)-CP was characterized by elemental analysis,thermogravime-try,IR,powder X-ray diffraction,and single-crystal X-ray diffraction.In Mo_(8)-CP,structural analysis reveals that Cu coordinates with BBTZ ligands to form an interlocked 1D chain.These chains are further bridged by(β-Mo_(8)O_(26))^(4-)to construct a 3D coordination polymer.Notably,(Emim)^(+)acts as a structure-directing agent,occupying the channels of the 3D coordination polymer.Based on this unique structure,the ion exchange properties of Mo_(8)-CP toward rare-earth ions were investigated.It has been found that the luminescent color of the material can be successfully regulat-ed by introducing Eu^(3+)or Tb^(3+)through ion exchange.CCDC:2475110,Mo_(8)-CP.展开更多
The morphology of active layer plays a critical role in determining the photovoltaic performance of organic solar cells(OSCs).However,binary blends often suffer from suboptimal phase separation,which limits the effici...The morphology of active layer plays a critical role in determining the photovoltaic performance of organic solar cells(OSCs).However,binary blends often suffer from suboptimal phase separation,which limits the efficiency of OSCs.Herein,two bridging polymer acceptors(PAs)—benzodithiophene-(2-ethylhexyl)oxy(BDT-C2C4)and benzodithiophene-octyloxy(BDT-C_(8))—are designed and synthesized by combining a benzodithiophene(BDT)unit as the donor moiety[poly({4,8-bis[5-(2-ethylhexyl)-4-fluorothiophen-2-yl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl}){5,8-bis[4-(2-butyloctyl)thiophen-2-yl]dithieno[3',2':3,4]},D18],and a 2,2′-((2Z,2′Z)-{[12,13-Bis(2-butyloctyl)-12,13-dihydro-3,9-dinonylthieno[2,3]thieno[3,2-b]pyrrolo[4,5-g]thieno[2,3-b]indole-2,10-diyl]bis(methanylylidene)}bis(3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(Y6)derivative as the acceptor moiety.BDT-C2C4 and BDT-C_(8) are functionalized with(2-ethylhexyl)oxy and octyloxy side chains on the BDT unit,respectively.Both PAs show complementary absorption and cascaded energy levels with the donor D18 and the acceptor 2,2′-((2Z,2′Z)-{[12,13-bis(3-ethylheptyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3″∶4′,5′]thieno[2′,3′∶4,5]pyrrolo[3,2-g]thieno[2′,3′∶4,5]thieno[3,2-b]indole-2,10-diyl]bis(meth⁃aneylylidene)}bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(N3),but BDT-C_(8) exhibits better compatibility with D18 and N3 compared to BDT-C2C4.When incorporated as a third component into the D18∶N3 blend,both PAs improve the active layer morphology.In particular,the D18∶N3∶BDT-C_(8) blend shows significantly optimized morphology,featuring reduced phase separation and a fibrous network structure.As a result,the device based on D18∶N3∶BDT-C_(8) achieves a power conversion efficiency of 18.18%,significantly higher than that of the device based on D18∶N3(ca.17.37%).This work presents a compatibilizer strategy for optimizing blend morphology towards high-performance ternary OSCs.展开更多
Four distinct coordination polymers(CPs)were successfully synthesized by altering solvent types and adjusting ligand concentrations,and their crystal structures were investigated.[Co(L)(FDCA)(H_(2)O)_(2)]·0.5H_(2...Four distinct coordination polymers(CPs)were successfully synthesized by altering solvent types and adjusting ligand concentrations,and their crystal structures were investigated.[Co(L)(FDCA)(H_(2)O)_(2)]·0.5H_(2)O(1)was synthesized as a 2D structure using Coas the metal source,methanol‑water(4∶6,V/V)as the solvent,and specific concentrations of 2,5‑furandicarboxylic acid(H_(2)FDCA)and 1,3,5‑triimidazole benzene(L).Adjusting to pure water and lowering the concentration of L yielded the 1D chain structure of[Co(HL)2(H_(2)O)_(2)](FDCA)_(2)·6H_(2)O(2).Using Cu(Ⅱ)as the metal source,methanol/water(9∶1,V/V)as the solvent,and specific concentrations of L and H2FDCA,the 1D chain structure of[Cu(L)(FDCA)(H_(2)O)]·2H_(2)O(3)was synthesized.Upon increasing the concentrations of L and H2FDCA,and switching the solvent to pure water,the 1D chain structure of[Cu(HL)_(2)(H_(2)O)_(2)](FDCA)_(2)·6H_(2)O(4)was obtained.This shows that changing the solvent and ligand concentrations can affect the structural changes of CPs.In addition,the solid‑state photoluminescence of CPs 1‑4 at room temperature was studied,and their morphological changes were observed via scanning electron microscopy.Density functional theory calculations revealed that the negative charge concentrates on the O and N atoms of the ligand,facilitating ligand‑metal ion coordination.CCDC:2403934,1;2403935,2;2403936,3;2403938,4.展开更多
Organic pollutants,a pivotal factor in water pollution,have persistently menaced the aquatic ecosystem,as well as the sustainable development of human health,economy,and society.Consequently,there is an urgent need fo...Organic pollutants,a pivotal factor in water pollution,have persistently menaced the aquatic ecosystem,as well as the sustainable development of human health,economy,and society.Consequently,there is an urgent need for advanced techniques to efficiently eliminate organic micropollutants from water.Here,we present the synthesis of three nonporous cavitand-crosslinked polymers capable of adsorbing diverse organic pollutants from aqueous solutions.These polymeric adsorbents exhibit outstanding adsorptive performance towards the tested micropollutants,characterized by high apparent adsorption rate constants(kobs)and maximum adsorption capacities(qmax,e).Notably,Compound NCCP-1 demonstrated a remarkable qmax,e of 459 mg/g for bisphenol A(BPA),ranking among the highest values reported for organic polymer adsorbents.In-depth investigation of the adsorption mechanism of the nonporous polymer revealed that it involves the recognition of pollutants by the deep cavities of the cavitand moieties and the interstitial spaces between them,primarily mediated by the hydrophobic effect.Furthermore,NCCP-1 was applied in situ water purification simulations and was proven to maintain its removal efficiency over more than four cycles,highlighting its potential for practical applications in water treatment.展开更多
The practical deployment of polyester-based solid electrolytes such as poly(ε-caprolactone)(PCL)is hindered by two inherent material-level constraints:the semicrystalline nature of PCL chains severely restricts segme...The practical deployment of polyester-based solid electrolytes such as poly(ε-caprolactone)(PCL)is hindered by two inherent material-level constraints:the semicrystalline nature of PCL chains severely restricts segmental mobility and limits ionic conductivity,whereas interfacial instability against lithium metal anodes jeopardizes long-term cycling.Based on orthogonal polymerization technology combined with electrolyte structural design concepts,this work achieved a one-step fabrication of a polyester-based block copolymer electrolyte(BCPE)system comprising fluorinated segments(PTFEA)and poly(ε-caprolactone)(PCL).Structurally,this design enables a dual breakthrough in electrochemical performance:on one hand,the introduction of fluorinated segments with steric hindrance effects can effectively disrupt the regular arrangement of the PCL main chain,reduce the crystallinity of PCL within the polymer electrolyte,and significantly enhance the segmental mobility of the polymer matrix;on the other hand,during the charge/discharge cycles of lithium batteries,fluorinated segments can induce the formation of a LiF-rich solid electrolyte interphase(SEI)through in situ decomposition reactions,achieving interface stabilization and homogeneous lithiumion deposition regulation.展开更多
Submission Papers appearing in the Journal comprise Editorials,Rapid Communications,Perspectives,Tutorials,Feature Articles,Reviews,Research Articles,which should contain original information,theoretical or experiment...Submission Papers appearing in the Journal comprise Editorials,Rapid Communications,Perspectives,Tutorials,Feature Articles,Reviews,Research Articles,which should contain original information,theoretical or experimental,on any topics in the field of polymer science and polymer material science.Papers already published or scheduled to be published elsewhere should not be submitted and certainly will not be accepted.展开更多
基金financially supported by the National Natural Science Foundation of China (Nos. 21674130, 51873234)Natural Science Foundation of Guangdong Province (No. 2017A030310 349)+1 种基金Fundamental Research Funds for the Central Universities (No. 17lgjc02)PetroChina Innovation Foundation (No. 2017D-5007-0505)
文摘Polymerizations of linear α-olefins(CnH2n, CH2=CH―R, R = Cn-2) catalyzed by early transition metals typically afford amorphous polymers with alkyl chains(Cn-2), while chain-straightening polymerizations of α-olefins with nickel-based catalysts produce semicrystalline polyolefins. Polymerizations of various α-olefins were carried out using an α-diamine nickel catalyst with a significantly distorted chelating ring. The influences of temperature, monomer concentration, and chain length of α-olefins on polyolefin microstructure were examined in detail. The α-diamine nickel catalyst realized highly regioselective 2,1-insertion of α-olefins regardless of reaction temperature and monomer concentration. Increased chain length of α-olefins led to the formation of more linear polyolefin.Semicrystalline polyolefins with high melting temperatures(Tm) were made from α-olefins through highly regioselective 2,1-insertion and precise chain-straightening.
基金financially supported by the National Basic Research Program of China(No.2015CB654700(2015CB654702))the National Natural Science Foundation of China(No.21801236)
文摘A series of pyrazolylimine ligated Co(II) and Fe(II) complexes with general formula of(PhC=N(C_6H_3(R_1)2-2,6)(C_3 HN_2(R_2)2-3,5)MtCl_2(R_1 = Me, R_2 = H, Mt = Co(1 a), Fe(2 a); R_1 = Me, R_2 = Me, Mt = Co(1b), Fe(2b); R_1 = iPr, R_2 = H, Mt = Co(1 c), Fe(2 c); R_1 = i Pr, R_2 = Me, Mt = Co(1 d), Fe(2 d); R_1 = i Pr, R_2 = Ph, Mt = Co(1 e), Fe(2 e)) were synthesized and thoroughly characterized.Determined by single crystal X-ray diffraction, complexes 1 b and 2 b revealed dimeric structures, in which distorted trigonal bipyramid geometries were adopted for each metal centers. In the presence of ethylaluminum sesquichloride(EASC), all the cobalt complexes displayed high activities in 1,3-butadiene polymerization, affording polybutadienes with predominant cis-1,4 contents(up to 97.0%).Influences of ligand structure and polymerization parameters on catalytic performance were investigated systematically. For pyrazolylimine iron(II) dichloride complexes, the catalytic activities and microstructures of the resultant polybutadienes were highly dependent on ligand structures and polymerization conditions. For complex 2 a, changing cocatalyst from trialkyl aluminums to methyl aluminoxane(MAO) led to an shift of selectivity from high cis-1,4-to trans-1,4-/1,2-manner. Being activated by MAO, complexes 2 a and 2 b gave trans-1,4-/1,2-binary polybutadienes, while complexes 2 c, 2 d, and 2 e afforded cis-1,4-enriched polymers.
基金financially supported by the National Natural Science Foundation of China(No.U1862206)Jilin Province Department of Education(No.JJKH20200665KJ)+3 种基金Dr.W.Zhao thanks for the financial support from China Postdoctoral Science Foundation(No.2021M701818)Shandong Provincial Natural Science Foundation,China(No.ZR2022QE237)Qingdao Postdoctoral Applied Research Project,PetroChina Company Limited(No.2020B-2711)H.Liu sincerely acknowledges the financial support from the Taishan Scholars Program。
文摘Through neodymium-mediated coordinative chain transfer copolymerizaiton(CCTcoP),polyisoprenes bearing dual hydroxylated mini-blocky chain-ends were prepared via a three-step strategy.Kinetic studies revealed that,the polymerization demonstrated typical features of CCTcoP across the whole polymerization process,i.e.,quasi-living polymerization characteristic,tunable molecular weights,narrow molecular weight distributions,and atom economies.Comparing to previously reported CCTP homopolymerization systems,the presence of oxygen-containing IpOAl polar comonomer slowed down chain transfer rates obviously,rendering slightly higher molecular weights of the resultant PIps and smaller Np(number of polymer chains per Nd atom)values.Moreover,to mimic the structure of natural rubber,the hydroxyl end groups can be facilely modified into phosphonate,amide,and UPy,whose structures were further confirmed by NMR spectra.Incorporation these functionalities could greatly improve the hydrophilic properties of the polymers,as revealed from the significantly reduced static water contact angles.
文摘Mechanistic transformation approach has been widely applied in polymer synthesis due to its unique feature combining structurally different polymers prepared by different polymerization mechanisms.Reported methods for the formation of block and graft copolymers through mechanistic transformation involve almost all polymerizations modes.However,certain polymerization processes require extensive purification processes,which can be time-consuming and problematic.Recent developments on controlled/living polymerizations involving radical and cationic mechanisms with the ability to control molecular weight and functionality led to new pathways for mechanistic transformations.In this mini-review,we systematically discussed relevant advances in the field through three main titles namely(i)from radical to cationic mechanism,(ii)from cationic to radical mechanism,and(iii)application of specific catalyst systems for both radical and cationic polymerizations.
基金financially supported by the National Natural Science Foundation of China(Nos.U21A20279 and 21774119)。
文摘We report herein the cationic polymerization of isobutylene(IB)under mild conditions is realized with a new binary initiation system generated by simply mixing a Lewis super acid Al(C_(6)F_(5))_(3) and a substituted phenol(RPhOH).Polymers with medium and/or high molecular weights(M_(W)=4.9×10^(4)-27.7×10^(4) g·mol^(-1))can be obtained in toluene and temperatures from-20℃to 0℃.NMR spectrum analysis and DFT sim ulation reveals the in situ generated acidic coordinating complex Ak(C_(6)F_(5))_(3)·RPhOH is the initiating active species,which fu rther tran sformed into the ion-pair[Al(C_(6)F_(5))_(3)ORPh]^(-)[PIB]^(+)of the active intermediates upon growing IB monomers where the counter anion[Al(C_(6)F_(5))_(3)R^(O)Ph]-coordinates to the macrocation via the phenoxy oxygen.The catalyst performances are the concert effects of the steric bulkiness and electronics of the counter anion on the coordinating strength to the macrocation,which is significant to the stability of the active species.
基金supported by the National Natural Science Foundation of China(Nos.52173005,21788102 and 21822102)the Ministry of Science and Technology of China(No.2021YFA1501600)+1 种基金the Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates(No.2019B030301003)the Fundamental Research Funds for the Central Universities.
文摘Multicomponent polymerizations(MCPs)are powerful tools to synthesize functional polymers with great structural diversity,low cost and high efficiency,which usually generate single polymer product.Herein,a robust one-pot diamines,CS_(2)and monoisocyanide-participated catalyst-free polymerization was developed at room temperature to produce polythiourea and thioformamide simultaneously in equal equivalent,which was featured with cheap monomers,simple operation and mild condition,affording various polythioureas with high Mws of up to 4.75×10^(4)g/mol in high yields of up to 98%.Polythioureas with varied chain composition and sequence-controlled structure could be synthesized in 62 g-scale from copolymerization or multicomponent tandem polymerization,enabling facile tuning of thermal property,crystallinity,mechanical property,and fluorescence.The abundant irregular hydrogen bonds endowed the polythioureas excellent glassy state self-healing property at room temperature or below 0℃.This polymerization provided an efficient and economic approach to access functional polythioureas.
基金financially supported by the National Natural Science Foundation of China(No.22171017).
文摘The alternating copolymerization of hydroxyalkyl vinyl ethers and dialkyl maleates is investigated by conventional radical polymerization and reversible addition-fragmentation chain transfer polymerization(RAFT).The influence of comonomer structure,comonomer feeding ratios,and monomer concentrations on the copolymerization and the copolymer structure have been investigated systematically.With 2-hydroxyethyl vinyl ether(HEVE)and dimethyl maleates(DMM)as comonomers,a well-defined alternating copolymer is prepared with M_(n)=3400 and M_(w)/M_(n)=1.93 up to 71.6% monomer.The alternating sequential chain structure of the copolymers has been proved by both NMR and matrixassisted laser desorption/ionization time-of-flight mass spectrometry(MALDI-TOF MS).The experimental reactivity ratios and theoretical calculated highest occupied molecular orbital and the lowest unoccupied molecular orbital of vinyl ethers and alkyl maleates support that these monomer pairs have tendency to form alternating copolymers.With 2-cyanopropan-2-yl N-methyl-N-(pyridin-4-yl)carbamodithioate as the RAFT agent,the molecular weight of HEVE and DMM copolymer increases with the monomer conversion,demonstrating a controlled radical polymerization feature with well-controlled molecular weight and relatively narrower molecular weight distribution.With alternating copolymer of HEVE and DMM as macro-CTA(M_(n)=5200 and M_(w)/M_(n)=1.46),both the chain extension with HEVE and DMM(M_(n)=10400 and M_(w)/M_(n)=1.72)and block copolymerization with vinyl acetate have been successfully achieved(M_(n)=8500 and M_(w)/M_(n)=1.52).
基金financially supported by the National Natural Science Foundation of China(No.21801002)the Overseas Students Innovation and Entrepreneurship Support Program Project of Anhui Province(No.2021LCX022)+1 种基金the Key R&D Projects in Anhui Province(No.2022i01020012)the Natural Science Foundation of Hefei(No.2022039)。
文摘Branched polyolefins with controllable topology structures were generated from the chain-walking(co)polymerizations of ethylene,1-pentene(1P)and 2-pentene(2P)using Brookhart-typeα-diimine Ni(II)-based catalysts possessing different para-substituted groups,{[(4-R-2-Et-6-Me-C6H2N=C)2Nap]NiBr2,Nap:1,8-naphthdiyl;R=CHMePh,Ni1;R=Ph,Ni2;R=H,Ni3}.The X-ray diffraction analysis demonstrated that the crystalline structure of Ni1′is in centrosymmetric dimer structure mode with the bimetallic Ni center connected by two bromide bridges.The para-sec-phenethyl moiety in the catalyst Ni1 obviously improved its catalytic performance and thermal stability in the ethylene polymerization.The Ni1/Et2AlCl system showed great catalytic activities(up to 7.73×106 g·mol-1·h-1)and achieved polyethylene(PE)with alkyl chains,including Me,Et,n-Pr,n-Bu,sec-Bu branches and longer chains(Lg).Compared with the 1-pentene polymerization,this catalyst system successfully mediated the polymerization of 2P to give highly branched polymers with approximately 195 branches/1000C possessing Me,Et,and n-Pr branches and a long methylene sequence due to the monomer isomerization.The Et branches derived from 2,3-insertion is slightly less than the sum of Me and n-Pr branches derived from 3,2-insertion,indicating that the 3,2-insertion mode is a slightly favorable pathway in the polymerization of 2P.
基金supported by the National Natural Science Foundation of China(22325102 and 52173005)the Ministry of Science and Technology of China(2021YFA1501600)+2 种基金the GuangDong Basic and Applied Basic Research Foundation(2023B1515040003)the Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates(2019B030301003)the Fundamental Research Funds for the Central Universities(2024ZYGXZR004 and 2022ZYGXZR107).
文摘Polythioureas with great potential in precious metal recovery materials,dielectric materials,light refractive materials,self-healing materials,and adhesives have become a group of popular polymer materials.While various synthetic approaches have been reported for different polythiourea structures,which generally involve expensive and toxic monomers,several polythiourea structures,such as asymmetric aromatic polythioureas,still have limited access.Herein,a base-catalyzed multicomponent polymerization(MCP)of elemental sulfur,diisocyanides,and diamines was developed,which was generally applicable for both aromatic amines with low reactivity and aliphatic amines with high nucleophilicity,affording polythioureas with great structural diversity,high Mw s of up to 107,700 g/mol and high yields of up to 99%.Moreover,aromatic polythioureas with different aromatic spacers installed on each side of the thiourea moiety could be facilely synthesized.Amine exchange reactions were studied for thiourea compounds or polythioureas,indicating that the C-N bonds of the thiourea moiety on the aromatic substitute side were more labile compared with those on the aliphatic substitute side,rendering the potential controllable degradation of different polythiourea structures.The polythioureas generally possess high thermal stability,with the glass transition temperatures ranging from 121 to 169℃.These polythioureas could efficiently absorb Hg2+from polluted water,and aromatic polythioureas generally showed better performance compared with semi-aromatic and aliphatic polythioureas.This work has hence provided a general synthetic approach for various aliphatic,aromatic,and semi-aromatic polythioureas with symmetric or asymmetric thiourea structures.The dynamic covalent bond nature of thioureas endowed these polymer materials with controllable degradation,making them sustainable functional polymer materials.
基金supported by the National Natural Science Foundation of China(22271197)the Guangdong Basic and Applied Basic Research Foundation(2025B1515020021,2023A15150-11578)+3 种基金the Shenzhen Science and Technology Program(RCYX20221008092924059,JCYJ20220531102601003)the Key-Area Research and Development Program of Guangdong Province(2024B0101040001)the 2035 Research Excellence Program of Shenzhen University(2023C001)the Instrumental Analysis Center of Shenzhen University for the support。
文摘The development of C-H activation-based polymerization strategies for the facile and efficient construction of novel functional fused heterocyclic polymers is an important but challenging task.Herein,we report a facile and atom-economical C-H activation/annulation polymerization(CAAP)approach that enables the in-situ formation of unique diheterocycle-fused polymers from readily available monomers based on the C-H activation of olefins.The rhodium-catalyzed polymerizations of fumaric acid and internal diynes proceed smoothly under mild conditions,producing a series of multisubstituted poly(dilactone)s with high molecular weights(M_(w)up to 109,600)in moderate to high yields of up to 98.4%.The presence of multiple aryl substituents around the dilactone units endows the resulting polymers with good solution processibility and readily tunable fluorescent properties.Most of the synthesized poly(dilactone)s exhibit aggregation-induced emission(AIE)properties,showing efficient aggregate-state fluorescence.The AIE-active poly(dilactone)can function as a good lysosome-specific fluorescent probe in biological imaging with low cytotoxicity.It is anticipated that these straightforward and economic CAAP reactions together with the structure-property relationship study in this work could promote the exploration of fused heterocyclic polymer materials with more diversified structures and advanced functionalities.
基金supported by the National Natural Science Foundation of China(22431004 and 22101088)the Fund of Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates(2023B1212060003)+1 种基金the Innovation and Technology Commission of Hong Kong(ITC-CNERC14SC01)the State Key Lab of Luminescent Materials and Devices,South China University of Technology(Skllmd-2024-19).
文摘Water,characterized by its safety,abundance,low cost,and sustainability,has garnered increasing attention in polymer synthesis.It has been utilized as a solvent or a comonomer in polymerizations based on triple-bond building blocks for the construction of functional polymers.Currently,distinct progress has been made;however,no such review was presented.This Review aims to summarize the progress in alkyne-based polymerizations in aqueous media with the“on-water”effect,water-involved alkyne-based polymerizations,and water-involved isocyanide-based polymerizations.The catalyst systems,reaction conditions,post-modification strategies,and the properties and applications of the resulting polymers are summarized.Furthermore,the challenges and opportunities in this field are briefly discussed.
基金support from the Natural Science Foundation of China(No.52322301,22131010,52131305,22271270,and 22071232)the Fundamental Research Funds for the Central Universities(WK3450000009)the University Synergy Innovation Program of Anhui Province(No.GXXT-2023-035).
文摘Vinyl polymers are widely used in modern society,but their all-carbon backbones make them highly resistant to degradation.One of the most effective solutions is to copolymerize them with cleavable monomers,resulting in degradable polymers that maintain thermal and mechanical properties similar to those of the original materials.Thionolactones have emerged as promising comonomers;however,only a few thionolactones are currently available for the preparation of degradable vinyl-based copolymers with unique reactivity.In this study,we developed a seven-membered,benzene-fused thionolactone,MBDT,as a comonomer and synthesized degradable polystyrene and its derivatives with thioester groups distributed along the chain through both radical and cationic copolymerizations.These copolymers can be degraded into short-chain fragments,which can then be recovered through oxidative repolymerization.Additionally,leveraging MBDT’s high copolymerization reactivity with styrene,we successfully conducted reversible addition−fragmentation chain transfer(RAFT)copolymerization,achieving controlled molecular weights(M_(n)’s)and narrow dispersities(Đ<1.2).Furthermore,we also successfully prepared degradable poly(p-methoxystyrene)via the cationic copolymerization of MBDT and p-methoxystyrene(MOS).
基金This research was made possible as a result of a generous grant from National Science Foundation of China(21822102,21774034,21490573,21490574,and 21788102)the Natural Science Foundation of Guangdong Province(2016A030306045 and 2016A030312002)the Innovation and Technology Commission of Hong Kong(ITC-CNERC14SC01)。
文摘Selenium-containing polymers with fascinating functionalities such as stimuli-responsive property,enzyme mimics,antioxidant activity,promotion of immune-cell activity,anticancer activity,and controlled delivery property,are highly desired,but rarely developed due to their underexplored synthetic methods.Herein,through careful design of monomeric structures and polymerization conditions,we report a series of catalyst-free multicomponent polymerizations(MCPs)of elemental selenium with aliphatic/aromatic diamines and diisocyanides that directly converted selenium to polyselenoureas with long-term stability,good solubility,well-characterized structures,and unique functionalities.The MCPs enjoyed broad monomer scope and fast conversion in 1 min,delivering 18 polyselenoureas with high molecular weights(M_(w)s up to 94,600 g/mol)in high yields(up to 99%).Furthermore,the polyselenoureas could be used for the extraction of Au^(3+)from mixed-metal ion solutions under practical conditions with high selectivity,sensitivity(<1μg/L),efficiency(>99.99%),and capacity(up to 665.60 mg·Au^(3+)/g)within 1 min.Further,the elemental gold was recoverable after the pyrolysis of the polymer complexes.
基金Supported by the National Natural Science Foundation of China(Nos.52293472,22473096 and 22471164)。
文摘Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynamic size and slower degradation.It is key to develop facile methods to large-scale synthesis of polymer rings with tunable compositions and microstructures.Recent progresses in large-scale synthesis of polymer rings against single-chain dynamic nanoparticles,and the example applications in synchronous enhancing toughness and strength of polymer nanocomposites are summarized.Once there is the breakthrough in rational design and effective large-scale synthesis of polymer rings and their functional derivatives,a family of cyclic functional hybrids would be available,thus providing a new paradigm in developing polymer science and engineering.
文摘The ionothermal reaction between CuCl_(2),1,4-bis(1,2,4-triazol-1-ylmethyl)benzene(BBTZ),and(NH_(4))_(6)Mo_(7)O_(24) in 1-ethyl-3-methylimidazolium bromide((Emim)Br)led to a new octamolybdate-based coordination polymer(Emim)2[Cu(BBTZ)_(2)(β-Mo_(8)O_(26))](Mo_(8)-CP).Mo_(8)-CP was characterized by elemental analysis,thermogravime-try,IR,powder X-ray diffraction,and single-crystal X-ray diffraction.In Mo_(8)-CP,structural analysis reveals that Cu coordinates with BBTZ ligands to form an interlocked 1D chain.These chains are further bridged by(β-Mo_(8)O_(26))^(4-)to construct a 3D coordination polymer.Notably,(Emim)^(+)acts as a structure-directing agent,occupying the channels of the 3D coordination polymer.Based on this unique structure,the ion exchange properties of Mo_(8)-CP toward rare-earth ions were investigated.It has been found that the luminescent color of the material can be successfully regulat-ed by introducing Eu^(3+)or Tb^(3+)through ion exchange.CCDC:2475110,Mo_(8)-CP.
文摘The morphology of active layer plays a critical role in determining the photovoltaic performance of organic solar cells(OSCs).However,binary blends often suffer from suboptimal phase separation,which limits the efficiency of OSCs.Herein,two bridging polymer acceptors(PAs)—benzodithiophene-(2-ethylhexyl)oxy(BDT-C2C4)and benzodithiophene-octyloxy(BDT-C_(8))—are designed and synthesized by combining a benzodithiophene(BDT)unit as the donor moiety[poly({4,8-bis[5-(2-ethylhexyl)-4-fluorothiophen-2-yl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl}){5,8-bis[4-(2-butyloctyl)thiophen-2-yl]dithieno[3',2':3,4]},D18],and a 2,2′-((2Z,2′Z)-{[12,13-Bis(2-butyloctyl)-12,13-dihydro-3,9-dinonylthieno[2,3]thieno[3,2-b]pyrrolo[4,5-g]thieno[2,3-b]indole-2,10-diyl]bis(methanylylidene)}bis(3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(Y6)derivative as the acceptor moiety.BDT-C2C4 and BDT-C_(8) are functionalized with(2-ethylhexyl)oxy and octyloxy side chains on the BDT unit,respectively.Both PAs show complementary absorption and cascaded energy levels with the donor D18 and the acceptor 2,2′-((2Z,2′Z)-{[12,13-bis(3-ethylheptyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3″∶4′,5′]thieno[2′,3′∶4,5]pyrrolo[3,2-g]thieno[2′,3′∶4,5]thieno[3,2-b]indole-2,10-diyl]bis(meth⁃aneylylidene)}bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(N3),but BDT-C_(8) exhibits better compatibility with D18 and N3 compared to BDT-C2C4.When incorporated as a third component into the D18∶N3 blend,both PAs improve the active layer morphology.In particular,the D18∶N3∶BDT-C_(8) blend shows significantly optimized morphology,featuring reduced phase separation and a fibrous network structure.As a result,the device based on D18∶N3∶BDT-C_(8) achieves a power conversion efficiency of 18.18%,significantly higher than that of the device based on D18∶N3(ca.17.37%).This work presents a compatibilizer strategy for optimizing blend morphology towards high-performance ternary OSCs.
文摘Four distinct coordination polymers(CPs)were successfully synthesized by altering solvent types and adjusting ligand concentrations,and their crystal structures were investigated.[Co(L)(FDCA)(H_(2)O)_(2)]·0.5H_(2)O(1)was synthesized as a 2D structure using Coas the metal source,methanol‑water(4∶6,V/V)as the solvent,and specific concentrations of 2,5‑furandicarboxylic acid(H_(2)FDCA)and 1,3,5‑triimidazole benzene(L).Adjusting to pure water and lowering the concentration of L yielded the 1D chain structure of[Co(HL)2(H_(2)O)_(2)](FDCA)_(2)·6H_(2)O(2).Using Cu(Ⅱ)as the metal source,methanol/water(9∶1,V/V)as the solvent,and specific concentrations of L and H2FDCA,the 1D chain structure of[Cu(L)(FDCA)(H_(2)O)]·2H_(2)O(3)was synthesized.Upon increasing the concentrations of L and H2FDCA,and switching the solvent to pure water,the 1D chain structure of[Cu(HL)_(2)(H_(2)O)_(2)](FDCA)_(2)·6H_(2)O(4)was obtained.This shows that changing the solvent and ligand concentrations can affect the structural changes of CPs.In addition,the solid‑state photoluminescence of CPs 1‑4 at room temperature was studied,and their morphological changes were observed via scanning electron microscopy.Density functional theory calculations revealed that the negative charge concentrates on the O and N atoms of the ligand,facilitating ligand‑metal ion coordination.CCDC:2403934,1;2403935,2;2403936,3;2403938,4.
基金supported by the National Natural Science Foundation of China(Nos.22322107,22101169 and 22071144)by Shanghai Scientific and Technological Committee(No.22010500300).
文摘Organic pollutants,a pivotal factor in water pollution,have persistently menaced the aquatic ecosystem,as well as the sustainable development of human health,economy,and society.Consequently,there is an urgent need for advanced techniques to efficiently eliminate organic micropollutants from water.Here,we present the synthesis of three nonporous cavitand-crosslinked polymers capable of adsorbing diverse organic pollutants from aqueous solutions.These polymeric adsorbents exhibit outstanding adsorptive performance towards the tested micropollutants,characterized by high apparent adsorption rate constants(kobs)and maximum adsorption capacities(qmax,e).Notably,Compound NCCP-1 demonstrated a remarkable qmax,e of 459 mg/g for bisphenol A(BPA),ranking among the highest values reported for organic polymer adsorbents.In-depth investigation of the adsorption mechanism of the nonporous polymer revealed that it involves the recognition of pollutants by the deep cavities of the cavitand moieties and the interstitial spaces between them,primarily mediated by the hydrophobic effect.Furthermore,NCCP-1 was applied in situ water purification simulations and was proven to maintain its removal efficiency over more than four cycles,highlighting its potential for practical applications in water treatment.
基金financially supported by the National Natural Science Foundation of China(No.52573079)the Innovation and Talent Recruitment Base of New Energy Chemistry and Device(No.B21003).
文摘The practical deployment of polyester-based solid electrolytes such as poly(ε-caprolactone)(PCL)is hindered by two inherent material-level constraints:the semicrystalline nature of PCL chains severely restricts segmental mobility and limits ionic conductivity,whereas interfacial instability against lithium metal anodes jeopardizes long-term cycling.Based on orthogonal polymerization technology combined with electrolyte structural design concepts,this work achieved a one-step fabrication of a polyester-based block copolymer electrolyte(BCPE)system comprising fluorinated segments(PTFEA)and poly(ε-caprolactone)(PCL).Structurally,this design enables a dual breakthrough in electrochemical performance:on one hand,the introduction of fluorinated segments with steric hindrance effects can effectively disrupt the regular arrangement of the PCL main chain,reduce the crystallinity of PCL within the polymer electrolyte,and significantly enhance the segmental mobility of the polymer matrix;on the other hand,during the charge/discharge cycles of lithium batteries,fluorinated segments can induce the formation of a LiF-rich solid electrolyte interphase(SEI)through in situ decomposition reactions,achieving interface stabilization and homogeneous lithiumion deposition regulation.
文摘Submission Papers appearing in the Journal comprise Editorials,Rapid Communications,Perspectives,Tutorials,Feature Articles,Reviews,Research Articles,which should contain original information,theoretical or experimental,on any topics in the field of polymer science and polymer material science.Papers already published or scheduled to be published elsewhere should not be submitted and certainly will not be accepted.
