In the field of organic solar cells(OSCs),side-chain engineering is a key strategy for developing high-performance non-fullerene small molecule acceptors(SMAs),which could adjust the material solubility and modulate t...In the field of organic solar cells(OSCs),side-chain engineering is a key strategy for developing high-performance non-fullerene small molecule acceptors(SMAs),which could adjust the material solubility and modulate the intermolecular stacking properties,profoundly impacting the film morphology and thus acting on the final power conversion efficiency(PCE) of the materials.In this study,two asymmetric acceptor molecules,Qx-Ph Br-BO and Qx-Ph Br-X,were synthesized by migrating the branching site of the outer side chain from the β-site to the γ-site.The branching site located at the γ-site could reduce the steric-hindrance effect and enhance the molecular aggregation behavior,giving rise to redshifted absorption and tight π-π stacking.Morphology analysis shows that the Qx-Ph Br-X-based devices have smoother surfaces and a phase-separated structure,which is more favorable for charge transport and extraction.The Qx-Ph Br-X-based devices exhibit balanced hole-electron mobility,efficient exciton dissociation,and low charge recombination.As a result,Qx-Ph Br-X with γ-site branching exhibits superior photovoltaic performance with a PCE of 17.16 %,which is significantly higher than that of Qx-Ph Br-BO at 16.28 %.These results highlight the importance of side-chain modifications for optimizing OSC efficiency and provide an important reference for precise tuning of side-chain structures in future molecular design.展开更多
As the proton transport channel and binder within the catalytic layer(CL),the physicochemical properties of the ionomer can affect the CL microstructure and performance of the membrane electrode assembly.In this paper...As the proton transport channel and binder within the catalytic layer(CL),the physicochemical properties of the ionomer can affect the CL microstructure and performance of the membrane electrode assembly.In this paper,we select ionomers with different side-chain lengths and investigate the effects of the side-chain structure and content of the ionomers on the performance of membrane electrode assembly(MEA).Electrochemical tests show that at a mass ratio of 10 wt.%of ionomer/Ir(I/Ir),long-side-chain(LSC)ionomer exhibits the best performance(2.141 V@2.00 A/cm^(2),while short-side-chain(SSC)ionomer is 2.208 V@2.00 A/cm^(2)).The MEA containing LSC ionomer shows better electrochemical performance than the SSC at the same I/Ir mass ratio,especially at high current density.The MEA containing LSC ionomer has a larger average pore size and porosity,which indicates that it may have better mass-transfer properties.From the analysis of voltage loss,it can be seen that LSC ionomers have a smaller ohmic impedance and mass transfer resistance than SSC ionomers.In conclusion,LSC ionomers are more conducive to water-gas transport,which can provide excellent water electrolysis performance.This article focuses on the optimization of ionomer side chains and content,which can enhance PEM water electrolysis performance at lower cost.展开更多
Traditional polymeric photocatalysts are typically constructed using aromatic building blocks to enhanceπ-conjugation.However,their inherent hydrophobicity and rigid structure lead to poor dispersibility in aqueous s...Traditional polymeric photocatalysts are typically constructed using aromatic building blocks to enhanceπ-conjugation.However,their inherent hydrophobicity and rigid structure lead to poor dispersibility in aqueous solutions,resulting in significant optical losses and exciton recombination.In this study,two series of six novel polymer photocatalysts(FLUSO,FLUSO-PEG10,FLUSO-PEG30;CPDTSO,CPDTSO-PEG10,CPDTSO-PEG30)are designed and synthesized by incorporating the hydrophilic,non-conjugated polyethylene glycol(PEG)chain,into both the main and side chains of polymers.By precisely optimizing the ratio of hydrophilic PEG segments,the water dispersibility is significantly improved while the light absorption capability of the polymer photocatalysts is well maintained.The experimental results confirm that the optimized FLUSO-PEG10 exhibits excellent photocatalytic hydrogen evolution rate,reaching up to 33.9 mmol/(g·h),which is nearly three times higher than that of fullyπ-conjugated counterparts.Water contact angles and particle size analyses reveal that incorporating non-conjugated segments into the main chains enhances the capacitance of the polymer/water interface and reduces particle aggregation,leading to improved photocatalyst dispersion and enhanced charge generation.展开更多
Ball milling modification was performed on Cs/X catalysts before or after cesium ion exchange.Multiple characterization results(such as pyridine-FTIR,XPS,and solid-state NMR)demonstrated that ball milling played a dis...Ball milling modification was performed on Cs/X catalysts before or after cesium ion exchange.Multiple characterization results(such as pyridine-FTIR,XPS,and solid-state NMR)demonstrated that ball milling played a distinct role in these two different preparation procedures of the catalyst.Ball milling performed after the cesium modification has a strong influence on the Cs/X structure and acid-base properties,which results in the enhancement of the catalytic performance for side-chain methylation of toluene with methanol.Detailed studies revealed that ball milling intensified the interactions between oxides and molecular sieves,which not only increased the dispersion of the Cs species but also generated some weaker basic centers.It is proposed that the new basic centers could be Si-O-Cs and Al-O-Cs,which are produced by breaking of the Si-O-Al bonds of the zeolite framework under the synergetic effect of ball milling and alkali treatment.These new active sites may help to promote the side-chain methylation reaction.However,excessive ball milling will lead to the vanishing of zeolite micropores,thus deactivating side-chain methylation activity,which indicates that microporosity plays a key role in side-chain methylation and individual basic centers cannot catalyze this reaction.展开更多
A series of hydroxide conductive polymers QTBMs carrying dense aromatic side-chain quaternary ammonium groups has been synthesized by using a new monomer of 3,3＇-di（3＂,5＂-dimethylphenyl）-4,4＇-difluorodiphenyl su...A series of hydroxide conductive polymers QTBMs carrying dense aromatic side-chain quaternary ammonium groups has been synthesized by using a new monomer of 3,3＇-di（3＂,5＂-dimethylphenyl）-4,4＇-difluorodiphenyl sulfone and other commercial monomers via polycondensation reaction, and subsequent bromination, quaternization and alkalization. The chemical structures of the ionomers were confirmed by 1H- and 13C-NMR spectroscopy. Water uptake, swelling ratio, hydroxide conductivity, the number of bonded water per ammonium group （A）, volumetric ion exchange capacity （IECvwet）, mechanical and thermal properties, and chemical stability were systematically evaluated for the series of QTBMs membranes. QTBMs showed IECs ranging from 1.02 meq·g-1 to 2.11 meq·g-1; in particular, QTBM-60 membrane with the highest IEC （2.11 meq·g-1） had very high hydroxide ion conductivity of 131.9 mS·cm-1 at 80 ℃, which was attributed to the well assembled nano-channels with distinct phase separation evidenced by small-angle X-ray scattering （SAXS）. It was found that the hydrated QTBMs membranes were mechanically stable with moderate water uptakes and swelling ratios, high chemical stability under the harsh alkaline conditions. This work provides a facile way to prepare anion exchange membranes （AEMs） with high performances for the application in alkaline fuel cells.展开更多
Side-chain alkylation of toluene with methanol is a green pathway to realize the one-step production of styrene under mild conditions,but the low selectivity of styrene is difficult to be improved with by-products of ...Side-chain alkylation of toluene with methanol is a green pathway to realize the one-step production of styrene under mild conditions,but the low selectivity of styrene is difficult to be improved with by-products of ethylbenzene and xylene.In this study,a new way is introduced to improve the catalytic performance by means of assisting basic compounds as co-catalysts during the toluene side-chain alkylation with methanol to styrene.As a result,high activity of side-chain alkylation appears over the basic Cs-modified zeolite catalysts prepared by ion exchange and impregnation methods.This high performance should be mainly attributed to two co-catalysis actions:(1)the promotion of basic compounds for methanol dehydrogenation to formaldehyde as the intermediate for side-chain alkylation;(2)the suppression of the styrene transfer hydrogenation on basic Cs-modified zeolites to avoid the formation of ethylbenzene.Especially for Cs_(2)O/CsX-ex catalyst,the addition of 2%mol/mol 2-picoline in reaction mixture could achieve both 12.3%toluene conversion and 84.1%styrene selectivity.Whereas the higher concentration of 2-picoline(>6%mol/mol)caused an inhibition to the catalytic activity because the excessive basic compound poisoned the combined acid-base pathway required for the side-chain alkylation process.In addition,two possible side-chain alkylation reaction routes on Cs-modified zeolite under the different 2-picoline absorption were described.展开更多
Long-alkyl tail triphenylene （TP） side-chain liquid crystalline polymers （SCLCPs） with different spacer length （P-m-TP, m = 2, 3, 4, 6, 8, which is the number of carbon atom in the flexible alkyl spacers） have b...Long-alkyl tail triphenylene （TP） side-chain liquid crystalline polymers （SCLCPs） with different spacer length （P-m-TP, m = 2, 3, 4, 6, 8, which is the number of carbon atom in the flexible alkyl spacers） have been successfully synthesized via free radical polymerization. The differential scanning calorimetry （DSC）, polarized light microscopy （POM）, ultraviolet-visible spectroscopy （UV- Vis）, wide-angle X-ray diffraction （WAXD） and small-angle X-ray scattering （SAXS） measurements were performed to investigate the influence of multiple effects on the self-organization behaviors of P-m-TP, including steric effect, decoupling effect and π-π stacking effect. The experimental results revealed that P-m-TP （m = 2, 3, 4） formed the columnar phase which was developed by the TP moieties and the main chain as a whole, suggesting that the side-chains had strong steric effect even though the number of spacer length （m） exceeded 4. In addition, the clearing points （Tis） of the polymers were above 300 ℃. When m = 6 and 8, the polymers displayed hexagonal columnar phase and exhibited the low Tis （91 and 80 ℃ respectively）, originating from the self-assembly of triphenylene due to the decoupling effect and π-π stacking effect. This work offers a viable and inspiring pathway to control the phase transition temperature and phase structure ofTP SCLCPs via simply tailoring the spacer length and increasing the alkyl tail length of TP.展开更多
Film morphology of emissive layers is crucial to the performance and stability of solution-processable organic light-emitting diodes(OLEDs). Compared to the interpenetration of conjugated polymer chain,small molecular...Film morphology of emissive layers is crucial to the performance and stability of solution-processable organic light-emitting diodes(OLEDs). Compared to the interpenetration of conjugated polymer chain,small molecular emitter with a flexible side chain always presents easily aggregation upon external treatment, and caused π-electronic coupling, which is undesirable for the efficiency and stability of deep-blue OLEDs. Herein, we proposed a side-chain coupling strategy to enhance the film morphological an emission stability of solution-processable small molecular deep-blue emitter. In contrary to “parent” MC8 TPA,the crosslinkable styryl and vinyl units were introduced as ended unit at the side-chain of Cm TPA and OEYTPA. Interestingly, Cm TPA and OEYTPA films present a relatively stable morphology and uniform deep-blue emission after thermal annealing(160 ℃) in the atmosphere, different to the discontinuous MC8 TPA annealed film. Besides, compared to the Cm TPA and OEYTPA ones, serious polaron formation in the MC8 TPA annealed film also negative to the deep-blue emission, according to transient absorption analysis. Therefore, both Cm TPA and OEYTPA annealed film obtained at 140 ℃ present an excellent deep-blue ASE behavior with a 445 nm, but absence for MC8 TPA ones, associated with the disruption of annealed films. Finally, enhancement of device performance based on Cm TPA and OEYTPA film(~40%)after thermal annealing with a similar performance curves also confirmed the assumption above. Therefore, these results also supported the effectiveness of our side-chain coupling strategy for optoelectronic applications.展开更多
A new liquid crystalline polyacetylene containing a phenyl benzoate mesogen (5) is synthesized,whose mesomorphic properties are found to be easily 'tunab1e' by simple mechanical perturbation. Thepolymerization...A new liquid crystalline polyacetylene containing a phenyl benzoate mesogen (5) is synthesized,whose mesomorphic properties are found to be easily 'tunab1e' by simple mechanical perturbation. Thepolymerization of 10- [ 4 - (4' -methoxyphenoxycarbonyl )phenoxycarbonyl] - 1 -decyne (4 ) in itiated by theWCl_6-Ph_4Sn/dioxane complex yields polymer 5 with a M_w of 28400. The molecular structure of 5 ischaracterized by NMR, IR, and UV spectroscopy and its liquid crystalline behavior is investigated by DSC,POM, and XRD analysis. Upon mechanical perturbation, 5 exhibits unusual agitation-induced high-strengthdisclinations, shear-induced inversion walls, and solidification-induced banded textures. Such phenomenahave been observed in the main-chain liquid crystalline polymers with rigid backbones, but have seldom beenreported for the side-chain liquid crystalline polymers with flexible backbones, suggesting that the rigidpolyacetylene backbone of 5 plays a constructive role in inducing the novel molecular alignments.展开更多
Side-chain modification is a proven effective approach for morphology manipulation in organic solar cells(OSCs).However,in-depth analysis and investigation involving side-chain modification towards morphology improvem...Side-chain modification is a proven effective approach for morphology manipulation in organic solar cells(OSCs).However,in-depth analysis and investigation involving side-chain modification towards morphology improvement,including molecular microstructure,orientating packing and aggregation are urgent for all-small-molecule(ASM)systems.Herein,employing a fluorine-modified two-dimension benzodithiophene(BDT)as central unit,we contrastively synthesized two small-molecule donors,namely BDT-F-SR and BDT-F-R,each welding alkylthio side-chains on thienyl of central BDT unit and the other grafted non-sulfuric alkyl side-chains.As predicted,the synergetic side-chain modification of fluorination and alkyl changeover triggers diverse molecular dipole moments and orientations,resulting in different molecular energy levels,thermal stabilities,molecular planarity and order.Eventually,together with the preeminent small-molecule acceptor Y6,BDT-F-R-based ASM OSCs obtain enhanced power conversion efficiency(PCE)of 13.88%compared to BDT-F-SR-based devices(PCE of 12.75%)with more suitable phase-separation and balanced carrier mobilities.The contrast results reveal that alkyl sidechains seem to be a more satisfactory partner for fluorine-modified 2D BDT-based small-molecule donors compared to alkylthio pendants,and highlight the significance of subtle side-chain modification for molecular structural order fun-tuning and morphology control,laying the foundation for efficient ASM OSCs.展开更多
This is a part of our systematic research work on polyimides with mesogenic unit side chain. In this study, a new 4＇-phenylpbenyl 4-（3＂,5＂-diaminobenzoyloxy）benzoate and polyimide were synthesized, and characteri...This is a part of our systematic research work on polyimides with mesogenic unit side chain. In this study, a new 4＇-phenylpbenyl 4-（3＂,5＂-diaminobenzoyloxy）benzoate and polyimide were synthesized, and characterized by FTIR, ^1H-NMR, inherent viscosity, mechanical properties, and solubility measurements. The diamine composed with mesogenic unit aryl ester groups and bipbenyl group with longer L/D ratio, was synthesized by two key steps. Firstly, the hydroxy group of 4-hydroxybenzoic acid was protected by acetoxy group for avoiding self- polymerization of 4-hydroxybenzoic acid, and then selectively hydrolyzed after esterification of carboxyl. Secondly, a selective catalysis hydrogenation was adopted to prevent the aryl ester from deoxidation. Based on this diamine, a novel polyimide was prepared by polycondensation of 4＇-phenylphenyl 4-（3＂, 5＂-diaminobenzoyloxy）benzoate and 4-aminophenyl ether（ODA） with 4, 4＇-oxydiphthalic anhydride（ODPA） in N-methyl-2-pyrrolidone （NMP）. The resulting polyimide with longer side chain showed better solubility and more regular structure. Its inherent viscosity is lower than that without side chains, but its modulus and strength not only maintained, even improved.展开更多
The morphological changes of a side-chain liquid-crystalline polymethacrylate during isotropization and liquid-crystallization transitions were studied by means of polarizing microscopy. These transitions were found t...The morphological changes of a side-chain liquid-crystalline polymethacrylate during isotropization and liquid-crystallization transitions were studied by means of polarizing microscopy. These transitions were found to be composed of the initiation of a new phase at local places of the old phase matrix and the growth of the new phase: domains. The kinetics of the liquid-crystallization of the polymer from an isotropic melt to a smectic mesophase was also investigated. The isothermal process of the transition can be described by the Avrami equation. The values of the Avrami exponent were found to be around 2.6. which is lower than the value usually obtained for crystallization transition of polymers, but larger than that reported for liquid-crystallization transition of main-chain polymers. These results may indicate the difference in growth geometry of new phase during transition between crystallization and liquid-crystallization in general and between liquid-crystallization of main-chain and side-chain polymers. It was found that the liquid-crystallization of the used side-chain polymethacrylate may occur at small undercoolings with high transformation rate similar to that of main-chain polymers and small-molecule liquid crystals, while the crystallization of polymers can only proceed at large undercoolings. These phenomena can be explained by the idea that the surface free energy of nucleus during liquid-crystallization transition is less than that for crystallization, and evidence was obtained from analysis of the temperature dependence of the transformation rate.展开更多
Photoluminescence properties and exciton decay dynamics in a porphyrin side-chain polymer, poly[porphyrin acrylate- acrylonitrile （abbreviated p[（por）A-AN]）, have been investigated by femtosecond time-resolved pho...Photoluminescence properties and exciton decay dynamics in a porphyrin side-chain polymer, poly[porphyrin acrylate- acrylonitrile （abbreviated p[（por）A-AN]）, have been investigated by femtosecond time-resolved photoluminescence spectroscopy. All the luminescences of p[（por）A-AN] films are due to the emissive decay of the photoexcited singlet excitons in the porphyrins. The luminescence efficiencies and lifetimes are increased for samples from pure films to dilute blend films. However, they are increased as the intrachain concentration of the porphyrin sidechain groups is decreased. The intrachain rotation motions of porphyrin sidechain groups result in the initial ultrafast luminescence decays, which are much faster than those due to the interchain interactions. All the samples show no significant red-shift and broadening of the transient luminescence spectra. The interchain and intrachain nonradiative exciton relaxation processes may play an important role in the luminescence dynamics in the p[（por）A-AN] films. The possible origin of different intrachain and interchain dynamic behaviours in p[（por）A-AN] films is discussed.展开更多
The morphological features of a side-chain liquid crystalline polymer during the mesophase transitions were investigated by using the DSC technique. The polymer used was polyacrylate with mesogens of three benzene rin...The morphological features of a side-chain liquid crystalline polymer during the mesophase transitions were investigated by using the DSC technique. The polymer used was polyacrylate with mesogens of three benzene rings attached to the main chain through a flexible spacer. A special two-phase texture was observed in the transition temperature range. Similar to main-chain liquid crystalline polymers the transition process of the side-chain liquid crystalline polymer was composed of an initiation of the new phase at local places of the old phase matrix and a growth process of the new phase domains.展开更多
The synthesis and upconverted fluorescent properties of a series of organic compounds with the structure: donor/bridge/acceptor, and different side-chains are reported. The results show that the compounds with differe...The synthesis and upconverted fluorescent properties of a series of organic compounds with the structure: donor/bridge/acceptor, and different side-chains are reported. The results show that the compounds with different side-chains exhibit different two-photon induced fluorescent properties, although they have the same main donor/bridge/acceptor structure.展开更多
Magnetic field-induced orientation of a chiral side chain liquid crystalline polyacrylate(P-11) was studied by using IR dichroism. For the investigated P-11, it has been shown thatthe magnetic alignment takes place ov...Magnetic field-induced orientation of a chiral side chain liquid crystalline polyacrylate(P-11) was studied by using IR dichroism. For the investigated P-11, it has been shown thatthe magnetic alignment takes place over the entire temperature range between its meltingpoint and clearing point and the orientation level is strongly temperature-dependent, thedevelopment with time of the magnetic orieatation follows an exponeotial-type relation,and the smectic phase state influences the thermal relaxation process in the absence of themagnetic field.展开更多
The incorporation of solid additive in photoactive layer as an effective strategy has been successfully employed to optimize the formation of a bi-continuous interpenetrating network morphology in blend bulk heterojun...The incorporation of solid additive in photoactive layer as an effective strategy has been successfully employed to optimize the formation of a bi-continuous interpenetrating network morphology in blend bulk heterojunction,which is a critical determinant of photovoltaic performance in organic solar cells(OSCs).However,the influence of additive side-chain length on the morphological evolution remains insufficiently understood.In this work,we propose two novel solid additives,1,3,5-tribromobenzene(TBB)and 1,3,5-tris(bromomethyl)benzene(TBMB)with different side-chain lengths.Theoretical calculations reveal that TBMB,featuring longer side-chain length,demonstrates stronger non-covalent intermolecular interaction with donors and acceptors compared to TBB,thereby favoring optimized molecular aggregation and crystallization behavior during film formation.As a result,the TBMB-treated device achieves a champion power conversion efficiency(PCE)of 17.92%in PM6:Y6 system,outperforming the TBB-treated counterpart(17.20%).Remarkably,TBMB exhibits universal effectiveness across other systems,achieving an exceptional efficiency of 20.04%in D18:L8-BO-based device.This work provides deep insights into the potential working mechanism of solid additives with precise side-chain length modulation,establishing a valuable additive side-chain effects for future research on morphology regulation in OSCs.展开更多
Naphthotubes are a class of macrocycles with welldefined cavities and are appealing for molecular recognition and smart materials.In this research,we report two types of hybridized naphthotubes(HNT)which were synthesi...Naphthotubes are a class of macrocycles with welldefined cavities and are appealing for molecular recognition and smart materials.In this research,we report two types of hybridized naphthotubes(HNT)which were synthesized through the condensation of a phenyl-bis-naphthalene(PN)tweezer and a bisnaphthalene cleft.The naphthyls attached to the PN tweezer can rotate around the single bonds to form conformational mixtures.When substituents are present at the ortho positions of the naphthyls,four atropisomers are formed.The water-soluble HNT could recognize phenylpyrimidine,phenyltetrazine,and drug intermediates effectively by adopting a syn conformation in aqueous environments(up to 10^(5)M^(-1)).Moreover,a series of shear-induced hydrogels have been prepared with the newly developed hybridized naphthotube,PEGs,and different transition-metal ions,which showed much stronger gelation properties compared to the previously reported amide naphthotubes.展开更多
The combination of mechanical and electrical properties in organic mixed ion-electron conductors(OMIECs)is crucial for their application in flexible,stretchable organic electrochemical transistors(OECT)intended for bi...The combination of mechanical and electrical properties in organic mixed ion-electron conductors(OMIECs)is crucial for their application in flexible,stretchable organic electrochemical transistors(OECT)intended for biological use.However,research on the simultaneous regulation of both the mechanical and electrical properties of OMIECs remains limited.In this work,poly[indacenodithiophene-alt-3,3'-dimethoxy-2,2'-bithiophene](IDT-OTOT)based polymers were designed to finetune the balance between their mechanical and electrical properties by varying the ratios of ethylene glycol to alkyl side chains(from 100%to 50%).Our findings indicate that when the ratio of ethylene glycol to alkyl side chains was reduced to 80%,the resulting polymer P80-gIDT-OTOT exhibited superior stretchability as well as an enhanced product of the charge carrier mobility and volumetric capacitance(μC*),along with improved device stability compared to other counterparts.The OECTs utilizing P80-gIDT-OTOT demonstrated outstanding performance and remarkable stability.Furthermore,OECTs constructed with stretched P80-gIDT-OTOT exhibited strain-independent characteristics within a stretching range of 10–50%,highlighting its excellent mechanical properties.This work establishes a structure-property relationship between side chains and the mechanical and electrical properties of OMIECs,which will be beneficial for advancing next-generation flexible and wearable bioelectronics.展开更多
Quantifying the hydrogen bond(H-bond)strength of polymers is essential for rational design of advanced materials.However,direct measurement remains challenging because of the structural complexity of polymers and the ...Quantifying the hydrogen bond(H-bond)strength of polymers is essential for rational design of advanced materials.However,direct measurement remains challenging because of the structural complexity of polymers and the weak nature of H-bonds.Vacuum-based singlemolecule force spectroscopy(Vac-SMFS)offers a new and precise approach for such measurements.Using polyallylamine(PAAm)as a model polymer,the intrinsic strength(i.e.,strength without external influences)of representative N―H…N H-bonds was quantified to be about 5.25 kJ·mol^(–1).Comparative Vac-SMFS analysis across different polymer systems revealed that the N―H…N H-bonds in PAAm are unexpectedly stronger than the N―H…O H-bonds in poly(N-isopropylacrylamide)(PNIPAM)and the O―H…O H-bonds in poly(hydroxyethyl methacrylate)(PHEMA).This trend contrasts with that of established small-molecule systems.These results highlight how side-chain length and spatial configuration dictate polymer H-bond strengths,expanding the fundamental knowledge of polymer interactions and enabling the rational design of next-generation functional materials.展开更多
基金the financial support by the Beijing Natural Science Foundation (No.Z230018)the Strategic Priority Research Program of the Chinese Academy of Sciences (No.XDB0520102)CAS Project for Young Scientists in Basic Research (No.YSBR-102)。
文摘In the field of organic solar cells(OSCs),side-chain engineering is a key strategy for developing high-performance non-fullerene small molecule acceptors(SMAs),which could adjust the material solubility and modulate the intermolecular stacking properties,profoundly impacting the film morphology and thus acting on the final power conversion efficiency(PCE) of the materials.In this study,two asymmetric acceptor molecules,Qx-Ph Br-BO and Qx-Ph Br-X,were synthesized by migrating the branching site of the outer side chain from the β-site to the γ-site.The branching site located at the γ-site could reduce the steric-hindrance effect and enhance the molecular aggregation behavior,giving rise to redshifted absorption and tight π-π stacking.Morphology analysis shows that the Qx-Ph Br-X-based devices have smoother surfaces and a phase-separated structure,which is more favorable for charge transport and extraction.The Qx-Ph Br-X-based devices exhibit balanced hole-electron mobility,efficient exciton dissociation,and low charge recombination.As a result,Qx-Ph Br-X with γ-site branching exhibits superior photovoltaic performance with a PCE of 17.16 %,which is significantly higher than that of Qx-Ph Br-BO at 16.28 %.These results highlight the importance of side-chain modifications for optimizing OSC efficiency and provide an important reference for precise tuning of side-chain structures in future molecular design.
基金Project(52271013)supported by the National Natural Science Foundation of ChinaProject(23DZ1200600)supported by the Science and Technology Innovation Action Plan of Shanghai,China。
文摘As the proton transport channel and binder within the catalytic layer(CL),the physicochemical properties of the ionomer can affect the CL microstructure and performance of the membrane electrode assembly.In this paper,we select ionomers with different side-chain lengths and investigate the effects of the side-chain structure and content of the ionomers on the performance of membrane electrode assembly(MEA).Electrochemical tests show that at a mass ratio of 10 wt.%of ionomer/Ir(I/Ir),long-side-chain(LSC)ionomer exhibits the best performance(2.141 V@2.00 A/cm^(2),while short-side-chain(SSC)ionomer is 2.208 V@2.00 A/cm^(2)).The MEA containing LSC ionomer shows better electrochemical performance than the SSC at the same I/Ir mass ratio,especially at high current density.The MEA containing LSC ionomer has a larger average pore size and porosity,which indicates that it may have better mass-transfer properties.From the analysis of voltage loss,it can be seen that LSC ionomers have a smaller ohmic impedance and mass transfer resistance than SSC ionomers.In conclusion,LSC ionomers are more conducive to water-gas transport,which can provide excellent water electrolysis performance.This article focuses on the optimization of ionomer side chains and content,which can enhance PEM water electrolysis performance at lower cost.
文摘Traditional polymeric photocatalysts are typically constructed using aromatic building blocks to enhanceπ-conjugation.However,their inherent hydrophobicity and rigid structure lead to poor dispersibility in aqueous solutions,resulting in significant optical losses and exciton recombination.In this study,two series of six novel polymer photocatalysts(FLUSO,FLUSO-PEG10,FLUSO-PEG30;CPDTSO,CPDTSO-PEG10,CPDTSO-PEG30)are designed and synthesized by incorporating the hydrophilic,non-conjugated polyethylene glycol(PEG)chain,into both the main and side chains of polymers.By precisely optimizing the ratio of hydrophilic PEG segments,the water dispersibility is significantly improved while the light absorption capability of the polymer photocatalysts is well maintained.The experimental results confirm that the optimized FLUSO-PEG10 exhibits excellent photocatalytic hydrogen evolution rate,reaching up to 33.9 mmol/(g·h),which is nearly three times higher than that of fullyπ-conjugated counterparts.Water contact angles and particle size analyses reveal that incorporating non-conjugated segments into the main chains enhances the capacitance of the polymer/water interface and reduces particle aggregation,leading to improved photocatalyst dispersion and enhanced charge generation.
文摘Ball milling modification was performed on Cs/X catalysts before or after cesium ion exchange.Multiple characterization results(such as pyridine-FTIR,XPS,and solid-state NMR)demonstrated that ball milling played a distinct role in these two different preparation procedures of the catalyst.Ball milling performed after the cesium modification has a strong influence on the Cs/X structure and acid-base properties,which results in the enhancement of the catalytic performance for side-chain methylation of toluene with methanol.Detailed studies revealed that ball milling intensified the interactions between oxides and molecular sieves,which not only increased the dispersion of the Cs species but also generated some weaker basic centers.It is proposed that the new basic centers could be Si-O-Cs and Al-O-Cs,which are produced by breaking of the Si-O-Al bonds of the zeolite framework under the synergetic effect of ball milling and alkali treatment.These new active sites may help to promote the side-chain methylation reaction.However,excessive ball milling will lead to the vanishing of zeolite micropores,thus deactivating side-chain methylation activity,which indicates that microporosity plays a key role in side-chain methylation and individual basic centers cannot catalyze this reaction.
基金supported by the National Natural Science Foundation of China(No.51173045)Student Research Program(SRP) Funds of South China University of Technology(Nos.105612015S165 and 105612016S198)
文摘A series of hydroxide conductive polymers QTBMs carrying dense aromatic side-chain quaternary ammonium groups has been synthesized by using a new monomer of 3,3＇-di（3＂,5＂-dimethylphenyl）-4,4＇-difluorodiphenyl sulfone and other commercial monomers via polycondensation reaction, and subsequent bromination, quaternization and alkalization. The chemical structures of the ionomers were confirmed by 1H- and 13C-NMR spectroscopy. Water uptake, swelling ratio, hydroxide conductivity, the number of bonded water per ammonium group （A）, volumetric ion exchange capacity （IECvwet）, mechanical and thermal properties, and chemical stability were systematically evaluated for the series of QTBMs membranes. QTBMs showed IECs ranging from 1.02 meq·g-1 to 2.11 meq·g-1; in particular, QTBM-60 membrane with the highest IEC （2.11 meq·g-1） had very high hydroxide ion conductivity of 131.9 mS·cm-1 at 80 ℃, which was attributed to the well assembled nano-channels with distinct phase separation evidenced by small-angle X-ray scattering （SAXS）. It was found that the hydrated QTBMs membranes were mechanically stable with moderate water uptakes and swelling ratios, high chemical stability under the harsh alkaline conditions. This work provides a facile way to prepare anion exchange membranes （AEMs） with high performances for the application in alkaline fuel cells.
基金Supported by the National Natural Science Foundation of China(#91534115).
文摘Side-chain alkylation of toluene with methanol is a green pathway to realize the one-step production of styrene under mild conditions,but the low selectivity of styrene is difficult to be improved with by-products of ethylbenzene and xylene.In this study,a new way is introduced to improve the catalytic performance by means of assisting basic compounds as co-catalysts during the toluene side-chain alkylation with methanol to styrene.As a result,high activity of side-chain alkylation appears over the basic Cs-modified zeolite catalysts prepared by ion exchange and impregnation methods.This high performance should be mainly attributed to two co-catalysis actions:(1)the promotion of basic compounds for methanol dehydrogenation to formaldehyde as the intermediate for side-chain alkylation;(2)the suppression of the styrene transfer hydrogenation on basic Cs-modified zeolites to avoid the formation of ethylbenzene.Especially for Cs_(2)O/CsX-ex catalyst,the addition of 2%mol/mol 2-picoline in reaction mixture could achieve both 12.3%toluene conversion and 84.1%styrene selectivity.Whereas the higher concentration of 2-picoline(>6%mol/mol)caused an inhibition to the catalytic activity because the excessive basic compound poisoned the combined acid-base pathway required for the side-chain alkylation process.In addition,two possible side-chain alkylation reaction routes on Cs-modified zeolite under the different 2-picoline absorption were described.
基金financially supported by the National Natural Science Foundation of China (No.21504075)Natural Science Foundation of Hunan Province (No.2017JJ3294)
文摘Long-alkyl tail triphenylene （TP） side-chain liquid crystalline polymers （SCLCPs） with different spacer length （P-m-TP, m = 2, 3, 4, 6, 8, which is the number of carbon atom in the flexible alkyl spacers） have been successfully synthesized via free radical polymerization. The differential scanning calorimetry （DSC）, polarized light microscopy （POM）, ultraviolet-visible spectroscopy （UV- Vis）, wide-angle X-ray diffraction （WAXD） and small-angle X-ray scattering （SAXS） measurements were performed to investigate the influence of multiple effects on the self-organization behaviors of P-m-TP, including steric effect, decoupling effect and π-π stacking effect. The experimental results revealed that P-m-TP （m = 2, 3, 4） formed the columnar phase which was developed by the TP moieties and the main chain as a whole, suggesting that the side-chains had strong steric effect even though the number of spacer length （m） exceeded 4. In addition, the clearing points （Tis） of the polymers were above 300 ℃. When m = 6 and 8, the polymers displayed hexagonal columnar phase and exhibited the low Tis （91 and 80 ℃ respectively）, originating from the self-assembly of triphenylene due to the decoupling effect and π-π stacking effect. This work offers a viable and inspiring pathway to control the phase transition temperature and phase structure ofTP SCLCPs via simply tailoring the spacer length and increasing the alkyl tail length of TP.
基金supported by the National Natural Science Foundation of China (Nos.22075136,61874053)National Key Research and Development Program of China (No.2020YFA0709900)+5 种基金Natural Science Funds of the Education Committee of Jiangsu Province (No.18KJA430009)Natural Science Foundation of Jiangsu Province (No.BK20200700)“High-Level Talents in Six Industries” of Jiangsu Province (No.XYDXX-019)Chain Postdoctoral Science Foundation (No.2021M692623)the open research fund from State Key Laboratory of Supramolecular Structure and Materials (No.sklssm202108)Anhui Province Key Laboratory of Environmentfriendly Polymer Materials and Anhui Province Key Laboratory of Optoelectronic Materials Science and Technology。
文摘Film morphology of emissive layers is crucial to the performance and stability of solution-processable organic light-emitting diodes(OLEDs). Compared to the interpenetration of conjugated polymer chain,small molecular emitter with a flexible side chain always presents easily aggregation upon external treatment, and caused π-electronic coupling, which is undesirable for the efficiency and stability of deep-blue OLEDs. Herein, we proposed a side-chain coupling strategy to enhance the film morphological an emission stability of solution-processable small molecular deep-blue emitter. In contrary to “parent” MC8 TPA,the crosslinkable styryl and vinyl units were introduced as ended unit at the side-chain of Cm TPA and OEYTPA. Interestingly, Cm TPA and OEYTPA films present a relatively stable morphology and uniform deep-blue emission after thermal annealing(160 ℃) in the atmosphere, different to the discontinuous MC8 TPA annealed film. Besides, compared to the Cm TPA and OEYTPA ones, serious polaron formation in the MC8 TPA annealed film also negative to the deep-blue emission, according to transient absorption analysis. Therefore, both Cm TPA and OEYTPA annealed film obtained at 140 ℃ present an excellent deep-blue ASE behavior with a 445 nm, but absence for MC8 TPA ones, associated with the disruption of annealed films. Finally, enhancement of device performance based on Cm TPA and OEYTPA film(~40%)after thermal annealing with a similar performance curves also confirmed the assumption above. Therefore, these results also supported the effectiveness of our side-chain coupling strategy for optoelectronic applications.
基金This project was in part supported by the Hong Kong Research Grants Council(HKUST597/95P&6149/97P)
文摘A new liquid crystalline polyacetylene containing a phenyl benzoate mesogen (5) is synthesized,whose mesomorphic properties are found to be easily 'tunab1e' by simple mechanical perturbation. Thepolymerization of 10- [ 4 - (4' -methoxyphenoxycarbonyl )phenoxycarbonyl] - 1 -decyne (4 ) in itiated by theWCl_6-Ph_4Sn/dioxane complex yields polymer 5 with a M_w of 28400. The molecular structure of 5 ischaracterized by NMR, IR, and UV spectroscopy and its liquid crystalline behavior is investigated by DSC,POM, and XRD analysis. Upon mechanical perturbation, 5 exhibits unusual agitation-induced high-strengthdisclinations, shear-induced inversion walls, and solidification-induced banded textures. Such phenomenahave been observed in the main-chain liquid crystalline polymers with rigid backbones, but have seldom beenreported for the side-chain liquid crystalline polymers with flexible backbones, suggesting that the rigidpolyacetylene backbone of 5 plays a constructive role in inducing the novel molecular alignments.
基金the Natural Science Foundation of Chongqing(cstc2019jcyj-msxmX0400)Youth Innovation Promotion Association Chinese Academy of Sciences(2020379)+2 种基金Chongqing Funds for Distinguished Young Scientists(cstc2020jcyj-jqX0018)General Program of National Natural Science Foundation of China(62074149)National Natural Science Foundation of China(51961165102).
文摘Side-chain modification is a proven effective approach for morphology manipulation in organic solar cells(OSCs).However,in-depth analysis and investigation involving side-chain modification towards morphology improvement,including molecular microstructure,orientating packing and aggregation are urgent for all-small-molecule(ASM)systems.Herein,employing a fluorine-modified two-dimension benzodithiophene(BDT)as central unit,we contrastively synthesized two small-molecule donors,namely BDT-F-SR and BDT-F-R,each welding alkylthio side-chains on thienyl of central BDT unit and the other grafted non-sulfuric alkyl side-chains.As predicted,the synergetic side-chain modification of fluorination and alkyl changeover triggers diverse molecular dipole moments and orientations,resulting in different molecular energy levels,thermal stabilities,molecular planarity and order.Eventually,together with the preeminent small-molecule acceptor Y6,BDT-F-R-based ASM OSCs obtain enhanced power conversion efficiency(PCE)of 13.88%compared to BDT-F-SR-based devices(PCE of 12.75%)with more suitable phase-separation and balanced carrier mobilities.The contrast results reveal that alkyl sidechains seem to be a more satisfactory partner for fluorine-modified 2D BDT-based small-molecule donors compared to alkylthio pendants,and highlight the significance of subtle side-chain modification for molecular structural order fun-tuning and morphology control,laying the foundation for efficient ASM OSCs.
基金We are grateful to the National Natural Science Foundation of China for financial support(project No.20274026)
文摘This is a part of our systematic research work on polyimides with mesogenic unit side chain. In this study, a new 4＇-phenylpbenyl 4-（3＂,5＂-diaminobenzoyloxy）benzoate and polyimide were synthesized, and characterized by FTIR, ^1H-NMR, inherent viscosity, mechanical properties, and solubility measurements. The diamine composed with mesogenic unit aryl ester groups and bipbenyl group with longer L/D ratio, was synthesized by two key steps. Firstly, the hydroxy group of 4-hydroxybenzoic acid was protected by acetoxy group for avoiding self- polymerization of 4-hydroxybenzoic acid, and then selectively hydrolyzed after esterification of carboxyl. Secondly, a selective catalysis hydrogenation was adopted to prevent the aryl ester from deoxidation. Based on this diamine, a novel polyimide was prepared by polycondensation of 4＇-phenylphenyl 4-（3＂, 5＂-diaminobenzoyloxy）benzoate and 4-aminophenyl ether（ODA） with 4, 4＇-oxydiphthalic anhydride（ODPA） in N-methyl-2-pyrrolidone （NMP）. The resulting polyimide with longer side chain showed better solubility and more regular structure. Its inherent viscosity is lower than that without side chains, but its modulus and strength not only maintained, even improved.
文摘The morphological changes of a side-chain liquid-crystalline polymethacrylate during isotropization and liquid-crystallization transitions were studied by means of polarizing microscopy. These transitions were found to be composed of the initiation of a new phase at local places of the old phase matrix and the growth of the new phase: domains. The kinetics of the liquid-crystallization of the polymer from an isotropic melt to a smectic mesophase was also investigated. The isothermal process of the transition can be described by the Avrami equation. The values of the Avrami exponent were found to be around 2.6. which is lower than the value usually obtained for crystallization transition of polymers, but larger than that reported for liquid-crystallization transition of main-chain polymers. These results may indicate the difference in growth geometry of new phase during transition between crystallization and liquid-crystallization in general and between liquid-crystallization of main-chain and side-chain polymers. It was found that the liquid-crystallization of the used side-chain polymethacrylate may occur at small undercoolings with high transformation rate similar to that of main-chain polymers and small-molecule liquid crystals, while the crystallization of polymers can only proceed at large undercoolings. These phenomena can be explained by the idea that the surface free energy of nucleus during liquid-crystallization transition is less than that for crystallization, and evidence was obtained from analysis of the temperature dependence of the transformation rate.
基金Project supported by the National Natural Science Foundation of China （Grant Nos 60478013, 20571089 and 10274107）, the Natural Science Foundation of Guangdong Province, China （Grant No 05101819）, and the Doctoral Program Foundation of Institute of Higher Education of China（Grant No 20040558031）.
文摘Photoluminescence properties and exciton decay dynamics in a porphyrin side-chain polymer, poly[porphyrin acrylate- acrylonitrile （abbreviated p[（por）A-AN]）, have been investigated by femtosecond time-resolved photoluminescence spectroscopy. All the luminescences of p[（por）A-AN] films are due to the emissive decay of the photoexcited singlet excitons in the porphyrins. The luminescence efficiencies and lifetimes are increased for samples from pure films to dilute blend films. However, they are increased as the intrachain concentration of the porphyrin sidechain groups is decreased. The intrachain rotation motions of porphyrin sidechain groups result in the initial ultrafast luminescence decays, which are much faster than those due to the interchain interactions. All the samples show no significant red-shift and broadening of the transient luminescence spectra. The interchain and intrachain nonradiative exciton relaxation processes may play an important role in the luminescence dynamics in the p[（por）A-AN] films. The possible origin of different intrachain and interchain dynamic behaviours in p[（por）A-AN] films is discussed.
基金The authors are grateful to the Director Foundation of Institute of Chemistry,Chinese Academy of Sciences and Science Foundation of Polymer Physics Laboratory,Chinese Academy of Sciences for supporting this work
文摘The morphological features of a side-chain liquid crystalline polymer during the mesophase transitions were investigated by using the DSC technique. The polymer used was polyacrylate with mesogens of three benzene rings attached to the main chain through a flexible spacer. A special two-phase texture was observed in the transition temperature range. Similar to main-chain liquid crystalline polymers the transition process of the side-chain liquid crystalline polymer was composed of an initiation of the new phase at local places of the old phase matrix and a growth process of the new phase domains.
基金This work was supported by thc grant for State Key Program of Chinaby the National Natural Science Foundation of China.
文摘The synthesis and upconverted fluorescent properties of a series of organic compounds with the structure: donor/bridge/acceptor, and different side-chains are reported. The results show that the compounds with different side-chains exhibit different two-photon induced fluorescent properties, although they have the same main donor/bridge/acceptor structure.
文摘Magnetic field-induced orientation of a chiral side chain liquid crystalline polyacrylate(P-11) was studied by using IR dichroism. For the investigated P-11, it has been shown thatthe magnetic alignment takes place over the entire temperature range between its meltingpoint and clearing point and the orientation level is strongly temperature-dependent, thedevelopment with time of the magnetic orieatation follows an exponeotial-type relation,and the smectic phase state influences the thermal relaxation process in the absence of themagnetic field.
基金supported by Natural Science Foundation of Guangdong Province,China(2025A1515011790)the Open Research Fund of Songshan Lake Materials Laboratory(2023SLABFK06)+4 种基金Guangdong Innovative and Entrepreneurial Research Team Program(2021ZT09L227)Guangdong Youth Top Talent Program(2021QN02L119)Education Department of Guangdong Province(No.2024ZDJS064)Guangdong Higher Education Letter[2024]No.30,Natural Science Foundation of Top Talent of SZTU(grant no.GDRC202307)Shenzhen Key Laboratory of Applied Technologies of Super-Diamond and Functional Crystals(ZDSYS20230626091303007).
文摘The incorporation of solid additive in photoactive layer as an effective strategy has been successfully employed to optimize the formation of a bi-continuous interpenetrating network morphology in blend bulk heterojunction,which is a critical determinant of photovoltaic performance in organic solar cells(OSCs).However,the influence of additive side-chain length on the morphological evolution remains insufficiently understood.In this work,we propose two novel solid additives,1,3,5-tribromobenzene(TBB)and 1,3,5-tris(bromomethyl)benzene(TBMB)with different side-chain lengths.Theoretical calculations reveal that TBMB,featuring longer side-chain length,demonstrates stronger non-covalent intermolecular interaction with donors and acceptors compared to TBB,thereby favoring optimized molecular aggregation and crystallization behavior during film formation.As a result,the TBMB-treated device achieves a champion power conversion efficiency(PCE)of 17.92%in PM6:Y6 system,outperforming the TBB-treated counterpart(17.20%).Remarkably,TBMB exhibits universal effectiveness across other systems,achieving an exceptional efficiency of 20.04%in D18:L8-BO-based device.This work provides deep insights into the potential working mechanism of solid additives with precise side-chain length modulation,establishing a valuable additive side-chain effects for future research on morphology regulation in OSCs.
基金supported by the National Natural Science Foundation of China(grant no.22101125).
文摘Naphthotubes are a class of macrocycles with welldefined cavities and are appealing for molecular recognition and smart materials.In this research,we report two types of hybridized naphthotubes(HNT)which were synthesized through the condensation of a phenyl-bis-naphthalene(PN)tweezer and a bisnaphthalene cleft.The naphthyls attached to the PN tweezer can rotate around the single bonds to form conformational mixtures.When substituents are present at the ortho positions of the naphthyls,four atropisomers are formed.The water-soluble HNT could recognize phenylpyrimidine,phenyltetrazine,and drug intermediates effectively by adopting a syn conformation in aqueous environments(up to 10^(5)M^(-1)).Moreover,a series of shear-induced hydrogels have been prepared with the newly developed hybridized naphthotube,PEGs,and different transition-metal ions,which showed much stronger gelation properties compared to the previously reported amide naphthotubes.
基金supported by the National Natural Science Foundation of China(Nos.T2422019,52263019,6227307)the Yunnan Fundamental Research Project(202301AT070313,2023Y0236)the Scientific Research and Innovation Project of Postgraduate Students in the Academic Degree of Yunnan University(KC-24248978).
文摘The combination of mechanical and electrical properties in organic mixed ion-electron conductors(OMIECs)is crucial for their application in flexible,stretchable organic electrochemical transistors(OECT)intended for biological use.However,research on the simultaneous regulation of both the mechanical and electrical properties of OMIECs remains limited.In this work,poly[indacenodithiophene-alt-3,3'-dimethoxy-2,2'-bithiophene](IDT-OTOT)based polymers were designed to finetune the balance between their mechanical and electrical properties by varying the ratios of ethylene glycol to alkyl side chains(from 100%to 50%).Our findings indicate that when the ratio of ethylene glycol to alkyl side chains was reduced to 80%,the resulting polymer P80-gIDT-OTOT exhibited superior stretchability as well as an enhanced product of the charge carrier mobility and volumetric capacitance(μC*),along with improved device stability compared to other counterparts.The OECTs utilizing P80-gIDT-OTOT demonstrated outstanding performance and remarkable stability.Furthermore,OECTs constructed with stretched P80-gIDT-OTOT exhibited strain-independent characteristics within a stretching range of 10–50%,highlighting its excellent mechanical properties.This work establishes a structure-property relationship between side chains and the mechanical and electrical properties of OMIECs,which will be beneficial for advancing next-generation flexible and wearable bioelectronics.
基金financially supported by the National Natural Science Foundation of China(No.22273079)Fundamental Research Funds for the Central Universities(No.2682025ZTPY004)。
文摘Quantifying the hydrogen bond(H-bond)strength of polymers is essential for rational design of advanced materials.However,direct measurement remains challenging because of the structural complexity of polymers and the weak nature of H-bonds.Vacuum-based singlemolecule force spectroscopy(Vac-SMFS)offers a new and precise approach for such measurements.Using polyallylamine(PAAm)as a model polymer,the intrinsic strength(i.e.,strength without external influences)of representative N―H…N H-bonds was quantified to be about 5.25 kJ·mol^(–1).Comparative Vac-SMFS analysis across different polymer systems revealed that the N―H…N H-bonds in PAAm are unexpectedly stronger than the N―H…O H-bonds in poly(N-isopropylacrylamide)(PNIPAM)and the O―H…O H-bonds in poly(hydroxyethyl methacrylate)(PHEMA).This trend contrasts with that of established small-molecule systems.These results highlight how side-chain length and spatial configuration dictate polymer H-bond strengths,expanding the fundamental knowledge of polymer interactions and enabling the rational design of next-generation functional materials.
