苯并菲盘状侧链液晶聚合物的大分子工程

盘状液晶聚合物兼具盘状液晶的光电性能和聚合物的柔韧性以及优异的成膜加工性能,有望发展成为新一代先进有机聚合物柔性光电功能材料.本文介绍苯并菲盘状侧链液晶聚合物的研究进展,主要结合我们研究组的工作,重点评述采用受控/活性自由基聚合方法可控合成这类侧链液晶聚合物以及对分子量效应和间隔基长度影响等基本问题的阐明.我们采用可逆加成-断裂链转移(RAFT)聚合第一次成功实现了分子量窄分布的苯并菲聚丙烯酸酯侧链盘状液晶聚合物的可控制备.首先提出盘单元局部簇集的分立短柱堆积(DCS)模型,合理解释了聚合度20左右出现的显著分子量效应,尤其揭示并提出了盘状侧链液晶聚合物的正耦合效应(PCE)理论,即短间隔基的较强耦合作用更有利于其有序柱状相的形成,与棒状侧链液晶聚合物经典的柔性长间隔基去耦合理论形成鲜明对照,补充了缺失的理论短板.基于这些原则,我们设计合成的丁氧基苯并菲聚丙烯酸酯侧链盘状液晶聚合物,经飞行时间谱(TOF)测试,表现出比文献报道值高1~2个数量级的载流子迁移率.进一步在手性客体分子掺杂诱导组装形成单手性螺旋结构聚合物复合物,以及拓扑受限环状聚合物和嵌段共聚物的受控制备等方面开展了比较系统的大分子工程实践.盘状侧链液晶聚合物的可控制备及其显著不同于棒状液晶聚合物体系的一些基本特征的阐明,为这类重要有机聚合物半导体材料的理性设计与可控合成提供理论指导,也为加速推进其光电器件化应用奠定基础.     

Influence of main chain on the phase behaviors of side-chain liquid-crystalline polymers with triphenylene mesogens of long alkyl tail substituents

A series of side-chain liquid-crystalline polymers (SCLCPs) containing triphenylene mesogen, in which the long alkyl tail Tp connected directly with main chain, were synthesized successfully. The chemical structures of the monomers were confirmed by ¹H NMR and mass spectrometry. The phase behaviors of polymers were investigated by a combination of techniques, including DSC, POM, 1D/2D WAXD, and SAXS. The experimental results suggested that the type of main chain played an important role in the LC phase structures of these polymers. Because of the steric effects of side chains and the coupling effects between the Tp moieties and the main chains, all the polymers exhibited columnar phase. However, the SCLCPs with poly(vinyl benzene methyl ether) or polynorbornene backbone displayed hexagonal columnar phase, while those with polyacrylate or polymethacrylate backbone presented columnar nematic phase, and the one with poly(vinyl benzoate) main chain showed rectangular columnar phase. Moreover, the clearing temperatures (Ti) changed with change in main chain. Especially, the Ti of the SCLCP with polymethacrylate backbone was above 300 °C. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 754–766     

Mesomorphic properties of copolyesters of 3,6-linked triphenylene-based units and polymethylene spacers

Main chain discotic liquid crystalline polymers consisting of triphenylene-based units and alkyl spacers (C8, C10 and C12), connected by ester linkages in the 3- and 6-positions of triphenylene, have been synthesized and their mesomorphic properties were studied by DSC, polarizing optical microscopy and X-ray diffraction. It was found that these polymers exhibit a hexagonal columnar (Col h ) mesophase with intracolumnar order over a wide temperature range. The clearing temperature decreases on increasing the spacer length. It was found that the clearing temperatures are rather higher than that of the corresponding triphenylene monomer having six hexyloxy chains. These polymers form an ordered columnar mesophase, while the corresponding monomeric mesogen shows a disordered columnar phase. In the polymeric system, the fluctuations of the disc-like units in the mesophase are restricted by the connection of the mesogenic units, which stabilizes the columnar mesophase.     

Mesomorphic properties of copolyesters of 3,6-linked triphenylene-based units and polymethylene spacers

Main chain discotic liquid crystalline polymers consisting of triphenylene-based units and alkyl spacers (C8, C10 and C12), connected by ester linkages in the 3- and 6-positions of triphenylene, have been synthesized and their mesomorphic properties were studied by DSC, polarizing optical microscopy and X-ray diffraction. It was found that these polymers exhibit a hexagonal columnar (Col_h) mesophase with intracolumnar order over a wide temperature range. The clearing temperature decreases on increasing the spacer length. It was found that the clearing temperatures are rather higher than that of the corresponding triphenylene monomer having six hexyloxy chains. These polymers form an ordered columnar mesophase, while the corresponding monomeric mesogen shows a disordered columnar phase. In the polymeric system, the fluctuations of the disc-like units in the mesophase are restricted by the connection of the mesogenic units, which stabilizes the columnar mesophase.     

Organic gels prepared from side‐chain liquid crystalline polymers without the spacer

A series of side‐chain liquid crystal polymers (SCLCPs) without the spacer, named poly[ω‐(4′‐n‐alkyl oxybiphenyl‐4‐oxy)methacrylate (PMBiCm, m = 1, 2, 4, 6, 8, 10, 12, 14, 16, and 18), have been synthesized. The novel polymer organogels were prepared by introducing PMBiCm into common organic solvents. Solubility and gel properties of polymer organogelators differ widely according to the nature of the solvents. In aromatic solvents, PMBiCm completely dissolved in solvent due to good compatibility between biphenyl mesogen group and aromatic solvents. Poly[ω‐(4′‐n‐alkyl oxybiphenyl‐4‐oxy)methacrylate were still insoluble in polar solvents such as acetone, ethanol, DMF, ethylene glycol, and n‐butanol. This behavior resulted from mismatch of solubility parameter between PMBiCm and solvent. Considering the factors of solvent, we have systematically studied 3 organic solvents with different polarities (butyl acetate, n‐butyl amine, and n‐heptane). It is found that the length of the alkoxy tail chain of the SCLCPs has significant influence on gelability and gel thermal stability. In further studies discussed by UV‐Vis spectroscopy, the results revealed that the π‐π stacking interaction of the biphenyl mesogens might be the key factor for guiding the self‐assembly processes and the polymer gel formation. This work is useful to comprehending physical mechanism of polymer organogels. Meanwhile, those expand SCLCPs to a wide range of applications.     

Donor/acceptor complex of triphenylene and trinitrotoluene on Au(111): a scanning tunneling microscopy study

The co-adsorption of trinitrotoluene (TNT), a typical π-electron acceptor, and triphenylene (TP), a typical π-electron donor, on a Au(111) surface was investigated by in situ Electrochemical Scanning Tunneling Microscopy (ECSTM). DFT calculations proved that parallelly stacked and well-overlapped TP and TNT molecules can form Donor-Acceptor dyads through intermolecular π-π charge transfer, which agree well with the experimental results in the present work.     

Side chain engineering and conjugation enhancement of benzodithiophene and phenanthrenequnioxaline based conjugated polymers for photovoltaic devices

A series of donor‐acceptor conjugated polymers incorporating benzodithiophene (BDT) as donor unit and phenanthrenequnioxaline as acceptor unit with different side chains have been designed and synthesized. For polymer P1 featuring the BDT unit and alkoxy chains substituted phenanthrenequnioxaline unit in the backbone, serious steric hindrance resulted in quite low molecular weight. The implementation of thiophene ring spacer in polymer P2 greatly suppressed the interannular twisting to extend the effective conjugation length and consequently gave rise to improved absorption property and device performance. In addition, utilizing the alkylthienyl side chains to replace the alkyl side chains at BDT unit in polymer P3 further enhanced the photovoltaic performance due to the increased conjugation length. For polymer P4, translating the alkoxy side chains at the phenanthrenequnioxaline ring into the alkyl side chains at thiophene linker group enhanced molecular planarity and strengthened π?π stacking. Consequently improved absorption property and increased hole mobility were achieved for polymer P4. Our results indicated that side chain engineering not only can influence the solubility of polymer but also can determine the polymer backbone planarity and hence the photovoltaic properties. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1915–1926     

Interfacial assembly of a series of cinnamoyl-containing bolaamphiphiles: spacer-controlled packing, photochemistry, and odd-even effect

A series of bolaamphiphiles with 4-hydroxycinnamoyl head groups and different length of the alkyl spacers (n = 6-12) were designed to investigate their photochemistry in the organized films obtained from the air/water interface. It has been found that both the length and odd-even number of the spacers can finely tune the molecular packing as well as the photochemistry. When the spacer length was changed from 6 to 12 methylene units, the assemblies changed from J aggregate to H aggregate. The molecules with even-numbered polymethylene spacer tend to form three-dimensional nanorod structure at the air/water interface. For the assembly of derivatives with odd-numbered spacers, diverse morphologies such as nanospirals and nanofibers were observed depending on the chain length and the surface pressures. The different packing of bolaamphiphiles could subsequently affect the photochemistry of the cinnamoyl groups in the organized films. The spacer effect in the assembly can be understood from the cooperation between H-bond of the phenolic hydroxyl and the amide groups, π-π stacking as well as the hydrophobic interactions of the alkyl spacer. A packing model was proposed to explain the phenomenon.     

Ionic interaction induced novel ordered columnar mesophases in asymmetric discotic triphenylene salts

Asymmetric triphenylene imidazolium salts with different spacer lengths were successfully synthesized through quarternization of ω-bromo-substituted triphenylenes with 1-methyl imidazole. The asymmetry in ω-bromo-substituted triphenylenes tended to destroy liquid crystallinity in the sample. However, highly ordered columnar mesophases with a lamellar microphase segregation were induced by ionic interactions among the imidazolium salts, and the lamellar morphology was visualized by transmission electron microscopy. On the basis of an X-ray diffraction study on shear oriented samples, a novel rectangular columnar phase with a plane group of pm was observed for a triphenylene imidazolium salt with a spacer length of C₁₁, while an oblique columnar phase was determined for a triphenylene imidazolium salt with a C₈ spacer. Due to the asymmetric molecular shape and ionic interactions in the triphenylene imidazolium salts, the columnar liquid crystalline phase was extended to below room temperature (c. -20°C) for samples with spacer lengths of C₈ and C₁₁.     

Functional Columnar Liquid Crystalline Phases From Ionic Complexes of Dendronized Polymers and Sulfate Alkyl Tails

We describe how cationic dendronized polymers of generations 1, and 2 and anionic monoalkyl tails can be combined by supramolecular ionic complexation into comb-like liquid crystalline polymers. The final structures in bulk of these supramolecular complexes were studied by differential scanning calorimetry (DSC), cross-polarized optical microscopy (CPOM), small angle x-rays scattering (SAXS) and transmission electron microscopy (TEM). The combination of these techniques allowed elucidating (i) that these complexes exhibit thermotropic behaviour, (ii) that various liquid crystalline structures in the 3–5 nm length scale can be obtained such as columnar rectangular, columnar tetragonal, columnar hexagonal and lamellar, depending both on alkyl tail length and polymer generation, (iii) that although the alkyl tails represent the majority phase in the columnar phases, they form the cylindric domains, and the dendronized polymers occupy the continuous domains. Therefore, upon selective cleavage of the alkyl tails in the columnar phases, the present self-assembly approach may constitute an efficient strategy towards the formation of porous organic matrices with ultra-dense pore size in the range of 2 to 4 nm.     

Controlled synthesis and microstructure tuning of PEG‐containing side‐chain discotic liquid crystalline block copolymers via RAFT polymerization

Liquid crystalline block copolymers (LCBCPs) are fascinating for their combining molecular level liquid crystalline orders and microphase separated multidomain morphologies. Here in this article, a series of PEG‐containing side‐chain discotic LCBCPs of PEG‐b‐P_m‐n with variant spacer length m = 6, 10 and degree of polymerization (DP) of discotic LC block from n = 10 to 45, have been well‐synthesized via reversible addition‐fragmentation chain‐transfer (RAFT) polymerization. The RAFT process mediated by macromolecular chain transfer agent (macroCTA) shows remarkable monomer concentration dependence. The influence of the introduced PEG block on the nano‐scale microphase‐segregation and mesophase organization is closely related to the side‐chain triphenylene (TP) discogens stacking mode dependent on the spacer length. Wherein, the PEG‐b‐P₆‐n series with a six‐methylene spacer exhibit consistent microphase separation with slightly disturbed yet ordered columnar structures. While for PEG‐b‐P₁₀‐n series with a longer ten‐methylene spacer, the columnar organization in the copolymers is even improved in contrast with the low order of randomly TP stacking in their corresponding homopolymers. This work offers a viable and inspiring pathway for controlled synthesis of block copolymers with bulky side groups, as well as enhances in‐depth understanding of the hierarchical superstructure organization in discotic units involved complex block copolymers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2544–2553     

苯并菲盘状液晶的合成、亲氟效应及分子对称性对介晶性的影响

New symmetrical and asymmetrical triphenylene-containing discotic liquid crystals with two different peripheral alkyl chains, known as sym-TP(OC6H13)3(OR)3 and asym-TP(OC6H13)3(OR)3, were synthesized. Their thermotropic liquid crystal properties were investigated through polarizing optical microscopy (POM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD) analyses. The asyrranetdcal discogens are 2,6,11-rialkoxy-3,7,10-trihexyloxytriphenylenes, with the alkyl chain carbon numbers varying from 3-10, 12, and 14, while the symmetrical compounds are 2,6,10-trialkyloxy-3,7,11-trihexyloxytriphenylene. Two fluoroalkoxy substituted triphenylene discogens, 2,6,10-td(4,4,4-trifluorobutoxy)-3,7,11-trihexyloxytriphenylene and its asymmetrical isomer 2,6,11-tri(4,4,4-trifluorobutoxy)-3,7,10-trihexyloxytdphenylene were prepared. These two compounds show higher melting and clearing points than their alkoxy analogs, which implies that fluorophilic effect exists in the formation and stabilization of discotic columnar mesophase. The triphenylene derivatives TP(OC6H13)3(OR)3 with two different peripheral chains, symmetrically or asymmetrically attached on triphenylene cores, have lower melting points and clearing points than those of the higher symmetrical compounds TP(OR)6 with the same total chain carbon numbers. The mixed-chain-triphenylenes with longer alkoxy chains (n=9,10,12,14) show columnarmesophase at room temperature.     

Side-chain tunability of furan-containing low-band-gap polymers provides control of structural order in efficient solar cells

The solution-processability of conjugated polymers in organic solvents has classically been achieved by modulating the size and branching of alkyl substituents appended to the backbone. However, these substituents impact structural order and charge transport properties in thin-film devices. As a result, a trade-off must be found between material solubility and insulating alkyl content. It was recently shown that the substitution of furan for thiophene in the backbone of the polymer PDPP2FT significantly improves polymer solubility, allowing for the use of shorter branched side chains while maintaining high device efficiency. In this report, we use PDPP2FT to demonstrate that linear alkyl side chains can be used to promote thin-film nanostructural order. In particular, linear side chains are shown to shorten π-π stacking distances between backbones and increase the correlation lengths of both π-π stacking and lamellar spacing, leading to a substantial increase in the efficiency of bulk heterojunction solar cells.     

Sandwich-type (phthalocyaninato)(porphyrinato) europium triple-decker nanotubes. Effects of the phthalocyanine peripheral substituents on the molecular packing

Three sandwich-type (phthalocyaninato)(porphyrinato) europium triple-decker complexes, namely Eu(2)(Pc)(2)(TClPP) (1), Eu(2)[Pc(β-OC(4)H(9))(8)](2)(TClPP) (2), and Eu(2)[Pc(β-OC(8)H(17))(8)](2)(TClPP) (3), have been designed, synthesized, and fabricated into nanotubes using nanoporous anodized aluminium oxide (AAO) membrane as the template. In particular, the effects of peripheral-substituents at the two phthalocyanine ligands in the triple-decker molecule on the molecular stacking relative to the alumina surface and the molecular packing mode in the nanotubes were clarified on the basis of the scanning electron microscopy (SEM), spectroscopic, and X-ray diffraction results. High-resolution TEM (HRTEM) images, in combination with the electronic absorption and XRD results, indicate that the discotic molecules of 1 without peripheral substituent on the phthalocyanine ligands form columnar structures on the alumina surface with homeotropic molecular stacking depending on the intermolecular π-π interactions in a head-to-tail manner. In good contrast, introduction of eight long octyloxy substituents at the peripheral-positions of the phthalocyanine ligands of 3 induces an increase in the interaction of the triple-decker molecules with the alumina surface, resulting in the formation of nanotubes with discotic molecules of 3 parallel stacking relative to the alumina surface depending on the intermolecular π-π interactions in a face-to-face manner. Most interestingly, introduction of eight shorter length butyloxy substituents at the peripheral-positions of the phthalocyanine ligands of 2 leads to the formation of nanotubes with discotic molecules of 2 parallel stacking relative to the alumina surface but depending on the intermolecular π-π interactions in a head-to-tail manner. X-Ray diffraction (XRD) data confirm the above-mentioned results.     

Dynamic Bonds Mediate π-π Interaction via Phase Locking Effect for Enhanced Heat Resistant Thermoplastic Polyurethane

Stimulus-responsive polymers containing dynamic bonds enable fascinating properties of self-healing, recycling and reprocessing due to enhanced relaxation of polymer chain/network with labile linkages. Here, we study the structure and properties of a new type of thermoplastic polyurethanes (TPUs) with trapped dynamic covalent bonds in the hard-phase domain and report the frustrated relaxation of TPUs containing weak dynamic bond andπ-πinteraction in hard segments. As detected by rheometry, the aromatic TPUs with alkyl disulfide in the hard segments possess the maximum network relaxation time in contrast to those without dynamic bonds and alicyclic TPUs. In situ FTIR and small-angle scattering results reveal that the alkyl disulfide facilitates stronger intermolecular interaction and more stable micro-phase morphology inπ-πinteraction based aromatic TPUs. Molecular dynamics simulation for pure hard segments of model molecules verify that the presence of disulfide bonds leads to strongerπ-πstacking of aromatic rings due to both enhanced assembling thermodynamics and kinetics. The enhancedπ-πpacking and micro-phase structure in TPUs further kinetically immobilize the dynamic bond. This kinetically interlocking between the weak dynamic bonds and strong molecular interaction in hard segments leads to much slower network relaxation of TPU. This work provides a new insight in tuning the network relaxation and heat resistance as well as molecular self-assembly in stimulus-responsive dynamic polymers by both molecular design and micro-phase control toward the functional applications of advanced materials.     

Bay区取代苝二酰亚胺分子构型及聚集调控:邻位甲基位阻效应

设计并合成了2种苝二酰亚胺分子PBI1和PBI2,研究了bay区的苯氧基团邻位甲基取代对分子构型及分子聚集的影响.通过对单晶结构的分析,发现邻位甲基的引入明显影响苝二酰亚胺分子构型,使得4个苯氧基呈中心对称分布.由于甲基的空间位阻效应,有效地减弱了分子间π-π相互作用,从而提高了分子的溶解性与溶液加工成膜性.研究结果表明,在π共轭分子结构中的关键位置引入小的甲基取代基能够显著调控分子的聚集行为,有效减少光电材料分子中非光电活性(增溶性基团)的含量,对光电材料分子的设计合成具有重要的指导意义.     

具有不同柱状结构的苯并菲盘状液晶化合物的合成及自组装

合成了3种含有不同长度烷基链的苯并菲盘状液晶化合物; 通过1H NMR 和 MALDI-TOF MS对其结构进行了表征; 利用差示扫描量热法(DSC)、热台偏光显微镜(POM)和小角X射线散射实验(SAXS)对3种液晶化合物的自组装行为进行了研究. 结果表明, 烷基链的长度对苯并菲盘状液晶化合物自组装结构的影响显著. 柔性链为辛基的苯并菲盘状液晶化合物自组装成六方柱状液晶相; 柔性链为十二烷基的化合物自组装成倾斜柱状液晶相; 而柔性链为十六烷基的化合物则未形成液晶相.     

Single-turn helix-coil strands stabilized by metal···metal and π-π interactions of the alkynylplatinum(II) terpyridyl moieties in meta-phenylene ethynylene foldamers

Dinuclear alkynylplatinum(II) terpyridyl complexes with oligomeric bridge consisting of five repeating meta-phenylene ethynylene (mPE) units have been found to exhibit a strong tendency to fold back onto themselves to form short helical strands through the stabilization of Pt···Pt and π-π interactions. The steric bulk of the terpyridine ligands and the length of the oligomeric bridge have been found to affect the extent of the intramolecular Pt···Pt interaction that governs the stabilization of the short helical strand in solution. Their folding properties via Pt···Pt and π-π stacking interactions have been studied by (1)H NMR, 2D ROESY NMR, electronic absorption, and emission spectroscopies.     

Imine polymers containing chiral nanohoops in the backbone obtained through [2 + 2] cyclocondensation

A simple method for synthesis of polymers containing shape persistent imine macrocycles as nanohoops in the main chain is studied. It is based on the cyclocondensation reaction carried out in solution and room temperature of triphenylamine-based tetraaldehyde compounds with (R,R)-trans-1,2-diaminocyclohexane. The pristine polymer P1 bearing long alkyl groups is soluble during the synthesis but becomes insoluble after precipitation due to the strong and multiple C H/π and π-π stacking intermolecular interactions from arene–arene species and entanglement and interpenetrating of flexible alkyl groups inside of rigid macrocycle hollow. Polymer without any solubilizing groups ( P2 ) separates during the polymerization as an insoluble material. Both polymers are amorphous and have good thermal and environmental stability. They have a low surface area because discrete nanovoids introduced by macrocycles are disconnected in the amorphous polymers and non-accessible for gas adsorption. Polymers have inherent luminescent properties due to triphenylamine groups and chirality derived from (R,R)-conformation of the cyclohexane skeleton. In presence of picric acid (PA), the polymer fluorescence in solid state or suspension is strongly quenched, thus the polymers can work as efficient fluorescent probes toward nitrophenolic compounds. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2565–2573     

Pentadecyl phenol- and cardanol-functionalized fluorescent, room-temperature liquid-crystalline perylene bisimides: effect of pendant chain unsaturation on self-assembly

A new perylene bisimide (PBI) building block based on pentadecyl phenol (PDP) or cardanol was developed, which upon esterification with 3,4,5-tridodecyloxy gallate resulted in highly emissive, room-temperature liquid-crystalline (LC) molecules. The self assembly in solution was studied in detail by NMR spectroscopy, UV/Vis absorption, and fluorescence spectroscopy. In solution both PDP- and cardanol-based PBI exhibited similar behavior. They were molecularly dissolved in chloroform (CHCl(3)) but formed rotationally displaced H-type aggregates that emitted at 640 nm in methylcyclohexane (MCH). Surface morphology in dropcast films were characterized using microscopic techniques such as SEM, TEM, and atomic force microscopy (AFM). The liquid-crystalline properties were studied using differential scanning calorimetry (DSC), polarized light microscopy (PLM), and variable-temperature X-ray (small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WXRD)) studies. Variable-temperature X-ray studies in the LC phase indicated strong π-π stacking interaction present in the PDP-based PBI derivative, whereas the stacking was absent in the LC phase of the cardanol-based PBI. The latter formed self-organized structures of extremely short length due to the presence of cis double bonds in the C15 alkyl side chain, whereas the saturated alkyl side chain in PDP could pack efficiently, thereby resulting in nanofibers that were several micrometers in length.