Role of ball milling during Cs/X catalyst preparation and effects on catalytic performance in side-chain alkylation of toluene with methanol

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.

Enhancing the side-chain alkylation of toluene with methanol to styrene over the Cs-modified X zeolite by the assistance of basic picoline as a co-catalyst

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.

MECHANICAL PERTURBATION INDUCED MOLECULAR ALIGNMENTS IN A SIDE-CHAIN LIQUID CRYSTALLINE POLYACETYLENE, POLY{10-[4-(4'-METHOXYPHENOXY-CARBOML)PHENOXYCARBONYL]-1-DECYNE}

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.

Efficient small-molecule donor with improved structural order and molecular aggregation enabled by side-chain modification

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.

A Novel Diamine,4'-Phenyiphenyi 4-(3",5"-Diaminobenzoyioxy)-benzoate and Longer Side-chain Polyimide

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.

MORPHOLOGICAL AND KINETIC STUDIES OF PHASE TRANSITIONS OF A SIDE-CHAIN LIQUID CRYSTALLINE POLYMER

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.

The effect of intermolecular interactions on photoluminescence of a porphyrin side-chain polymer

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.

MORPHOLOGICAL STUDIES OF A THERMOTROPIC SIDE-CHAIN LIQUID CRYSTALLINE POLYMER DURING MESOPHASE TRANSITIONS

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.

Two-photon Pumped Up-conversion Lasing Properties of A Series of Organic Salts with Different Side-chains

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.

STUDY ON MAGNETIC FIELD-INDUCED 0RIENTATI0N OF A CHIRAL SIDE-CHAIN LIQUID CRYSTAL POLYACRYLATE USING INFRARED DICHROISM

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.

Polymer donors with hydrophilic side-chains enabling efficient and thermally-stable polymer solar cells by non-halogenated solvent processing

Polymer solar cells(PSCs)with high power conversion efficiency(PCE)and environment-friendly fabrication are the main requirements enabling their production in industrial scale.While the use of non-halogenated solvent processing is inevitable for the PSC fabrication,it significantly reduces the processability of polymer donors(PDS)and small-molecule acceptors(SMAs).This often results in unoptimized blend morphology and limits the device performance.To address this issue,hydrophilic oligoethylene glycol(OEG)side-chains are introduced into a PD(2EG)to enhance the molecular compatibility between the PD and L8-BO SMA.The 2EG PD induces higher crystallinity and alleviates phase separation with the SMA compared to the reference PD(PM7)with hydrocarbon side-chains.Consequently,the 2EG-based PSCs exhibit a higher PCE(15.8%)than the PM7-based PSCs(PCE=14.4%)in the ortho-xylene based processing.Importantly,benefitted from the reduced phase separation and increased crystallinity of 2EG PDS,the 2EG-based PSCs show enhanced thermal stability(84%of initial PCE after 120 h heating)compared to that of the PM7-based PSCs(60%of initial PCE after 120 h heating).This study demonstrates the potential of OEG side-chain-incorporated materials in developing efficient,stable,and eco-friendly PSCs.

Designing high-performance nonfused ring electron acceptors via side-chain engineering

The side-chain has a significant influence on the optical properties and aggregation behaviors of the organic small molecule acceptors,which becomes an important strategy to optimize the photovoltaic performance of organic solar cells.In this work,we designed and synthesized three brand-new nonfused ring electron acceptors(NFREAs)OC4-4Cl-Ph,OC4-4Cl-Th,and OC4-4Cl-C8 with hexylbenzene,hexylthiophene,and octyl side chains on theπ-bridge units.Compared with OC4-4Cl-Ph and OC4-4Cl-Th,OC4-4Cl-C8 with linear alkyl side chain has more red-shift absorption,which is conducive to obtaining higher short-circuit current density.Additionally,the OC4-4Cl-C8 film exhibits a longer exciton diffusion distance,and the D18:OC4-4Cl-C8 blend film displays faster hole transfer,weaker bimolecular recombination,and more efficient exciton transport.Furthermore,The D18:OC4-4Cl-C8 blend films may effectively form interpenetrating networks that resemble nanofibrils,which can facilitate exciton dissociation and charge transport.Finally,OC4-4Cl-C8-based devices can be created a marvellously power conversion efficiency(PCE)of 16.56%,which is much higher than OC4-4Cl-Ph(12.29%)-and OC4-4Cl-Th-based(11.00%)ones,being the highest PCE among the NFREA based binary devices.All in all,we have validated that side-chain engineering is an efficient way to achieve high-performance NFREAs.

Methylthio side-chain modified quinoidal benzo-[1,2-b:4,5-b']dithiophene derivatives for high-performance ambipolar organic field-effect transistors

Quinoidal small molecule semiconductors hold huge potential in ambipolar organic field-effect transistors(OFETs)and organic spintronic devices.Here,two quinoidal molecules with methylthio side chains were synthesized to develop molecular semiconductors with high ambipolar mobility,designated QBDTS and QTBDTS.The theoretical calculation results reveal that QBDTS has a closed-shell structure while QTBDTS showed an open-shell structure with a biradical character(y0)of 0.46 and its magnetic properties were further investigated using electron paramagnetic resonance(EPR)and superconducting quantum interference device(SQUID)methods.The methyl side chains showed a large impact on the molecular orbital levels.The HOMO/LUMO levels of QBDTS and QTBDTS were measured to be-5.66/-4.56 and-5.27/-4.48 eV,respectively,which are favorable for ambipolar charge transport in OFETs.Importantly,the spin-coated QBDTS displayed hole and electron mobilities of 0.01 and 0.5 cm^(2)V^(-1)s^(-1)while QTBDTS showed a record high hole mobility of 1.8 cm^(2)V^(-1)s^(-1)and electron mobility of 0.3 cm^(2)V^(-1)s^(-1).Moreover,comparative studies of the thin film morphologies also manifested the beneficial influence of methyl side chains on film crystallinity and molecule orientation.These results strongly proved that methyl side chain engineering can be a simple but efficient strategy for modulating electronic properties and molecular stacking behaviors.This work also represents a big advancement for quinoidal molecular semiconductors in ambipolar OFET applications.

Side-Chain Engineering of Non-Fullerene Acceptors with Trialkylsilyloxy Groups for Enhanced Photovoltaic Performancet

Side-chain engineering has emerged as a highly effective strategy for tailoring the aggregation behavior and charge transport properties of non-fullerene small molecule acceptors(SMAs).In this study,we designed and synthesized two SMAs,namely BTPSi-Bu and BTPSi-Pr,respectively incorporating tributylsilyloxy and trisopropylsilyloxy groups in their outer positions.Notably,BTPSi-Bu exhibited better planarity,crystallization,and favorable phase separation when paired with PM6 donor polymer compared to its counterpart,BTPSi-Pr.The resulting organic solar cells,utilizing the PM6:BTPSi-Bu blend,demonstrated a remarkable power conversion efficiency of 17.41%and a high open-circuit voltage of 0.859 V.These findings underscore the significance of integrating trialkylsilyloxy side chains into SMAs as a rational design approach for enhancing the performance of photovoltaic systems.

Manipulating noncovalent conformational lock via side-chain engineering for luminescence at aggregate level

The unfavorable photochemical processes at the molecular level have become a bar-rier limiting the use of aromatic amides as high-performance luminescent materials.Herein,we propose a reliable strategy for manipulating noncovalent conformational lock(NCL)via side-chain engineering to burst out eye-catching luminescence at the aggregate level.Contrary to the invisible emission in dilute solutions,dyad OO with a three-centered H-bond gave the wondrous crystallization-induced emis-sion with a quantum yield of 66.8%and clusterization-triggered emission,which were much brighter than those of isomers.Theoretical calculations demonstrate that crystallization-induced planarized intramolecular charge transfer(PICT),con-formation rigidification,and through-space conjugation(TSC)are responsible for aggregate-state luminescence.Robust NCL composed of intramolecular N-H⋅⋅⋅Ointeractions could boost molecular rigidity and planarity,thus greatly facilitating PICT and TSC.This study would inspire researchers to design efficient luminescent materials at the aggregate level via rational conformational control.

Side-chain engineering for regulating structure and properties of a novel visible-light-driven perylene diimide-based supramolecular photocatalyst

Systematic and in-depth explorations of the effects of side-chain modulation on the molecular assembly,optoelectronic properties,and photocatalytic properties of supramolecular systems,as well as the kinetics of charge separation and migration in these systems,are rare.In this study,a novel supramolecular photocatalyst with an alkoxy side chain(S-EPDI)was successfully developed through subtle design of the short and linear alkoxyl side chains,affording a phenol degradation efficiency approximately four times that of the counterpart with an alkyl side chain(S-APDI).Notably,combined density functional theory(DFT)calculations,absorption spectroscopy,and other characterizations revealed that the perylene diimide(PDI)molecular units,throughπ-πstacking,formed a unique rotationally offset stacked supramolecular structure,exhibiting a significant dipole moment.This gave rise to the formation of a larger inherent electric field within S-EPDI compared to S-APDI.Moreover,the study quantitatively demonstrated that a stronger inherent electric field and lower rate of surface charge recombination facilitate efficient separation of the photogenerated carriers.Therefore,the side-chain molecular engineering method employed in this study offers an effective approach for modulating the kinetics of charge migration.

Side-chain engineering of high-efficiency conjugated polymer photovoltaic materials

In recent years,conjugated polymers have attracted great attention in the application as photovoltaic donor materials in polymer solar cells(PSCs).Broad absorption,lower-energy bandgap,higher hole mobility,relatively lower HOMO energy levels,and higher solubility are important for the conjugated polymer donor materials to achieve high photovoltaic performance.Side-chain engineering plays a very important role in optimizing the physicochemical properties of the conjugated polymers.In this article,we review recent progress on the side-chain engineering of conjugated polymer donor materials,including the optimization of flexible side-chains for balancing solubility and intermolecular packing(aggregation),electron-withdrawing substituents for lowering HOMO energy levels,and two-dimension(2D)-conjugated polymers with conjugated side-chains for broadening absorption and enhancing hole mobility.After the molecular structural optimization by side-chain engineering,the2D-conjugated polymers based on benzodithiophene units demonstrated the best photovoltaic performance,with powerconversion efficiency higher than 9%.

Recent developments in peptide ligation independent of amino acid side-chain functional group

Chemical synthesis of peptides and proteins has evolved into an indispensable tool for chemical biology. Peptide ligation is a straightforward technique for joining two short peptide fragments together via a native peptide bond to afford a larger natural peptide or protein. However, the junction sites are limited to several specific amino acids because most peptide ligations involve participation of the side-chain functional groups of the junction-site amino acids. To overcome such intrinsic limitations, "general"peptide ligations which do not rely on the side-chain functional group have been developed. This review summarized the recent developments in peptide ligations that are independent of side-chain functional group of ligation-junction-site amino acid.

Synthesis and Properties of Hydroxide Conductive Polymers Carrying Dense Aromatic Side-chain Quaternary Ammonium Groups

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.

Multiple Effects Tailoring the Self-organization Behaviors of Triphenylene Side-chain Liquid Crystalline Polymers via Changing the Spacer Length

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.