基于多元大环的分子机器及其功能化超分子聚合物

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英文题名：Synthesis and Properties of Macro-cycle Based Functional Supramolecular Pseudorotaxane Polymer 作者：孙如意 论文级别：博士 学科专业名称：应用化学 中文关键词：合成 ; 分子机器 ; 超分子 ; 聚合物 英文关键词：Synthesis ; Molecular machine ; Pseudorotaxane ; Supramolecular ; Polymer 学位年度：2013 导师：苏建华 ; 田禾 学科代码：081704 学位授予单位：华东理工大学 论文提交日期：2013-05-29

摘要

超分子聚合物是聚合物排列的单体单元通过可逆和高取向二级作用连接到一起,形成在稀溶液、浓溶液及大体积状态下具有聚合物性质的物质。聚合度、聚合物链寿命、聚合物组成等结构和动态参数决定了聚合物的性质,而这些性质是非共价键作用强弱的功能化表现,可以可逆调节。这就导致了超分子聚合物材料具有对外界刺激的响应能力,这是传统超分子所不具备的。超分子聚合物的这方面特性,引起了新型化合物的不断涌现,同时促进研究者将材料科学与超分子化学联合研究。在另一方面,要想达到聚合物具有众多重要性质的目标,我们需要引入可逆非共价键将重复单元连接成链。所有这些性质都具有重要的应用价值,因此,超分子聚合物成为我们研究的不二选择。
     第一章综述了基于多种大环的分子机器的超分子聚合物的最新研究进展。评述了超分子聚合物的定义,外界响应超分子聚合物的种类及其潜在的应用前景。重点指出基于分子机器的超分子聚合物是最具有应用前景超分子聚合物类型之一,同时介绍了基于环糊精、杯芳烃、葫芦脲和其他大环体系的超分子聚合物。最后提出了课题。
     第二章相对于已经广泛系统研究的常用主体单体的冠醚和环糊精而言,超分子聚合物中基于杯芳烃衍生物的主体客体相互作用的研究至今较少。我们研究了经由两个单体形成的新型荧光超分子聚合物,它包含基于对磺酸基杯[4]芳烃的同类双头连接体和荧光团修饰具联吡啶和二氨基连接体。这个荧光超分子聚合物具有电化学氧化还原和酸碱变化双响应的特性,同时伴随着由不同刺激引发形成的两种不同的拟轮烷单聚体。
     第三章π体系间的电荷转移(CT)作用和给体受体间作用已经发展成为非共价键作用的一个重要研究分支,被广泛应用于自组装体系的设计和合成中。将超分子体系的众多特性与超分子聚合物联系到一起,对于可控改变聚合物性质的研究具有重要意义。我们构建了一个基于主体稳定的联吡啶双阳离子与荧光团修饰二甲氨基单元间电荷转移作用的新型荧光超分子聚合物体系。通过将单体的供电子单元与邻近得电子单元包结在CB[8]中,形成CB[8]稳定的分子间CT作用,我们可以得到目标聚合物。于此同时,由于聚合物的性质受到相应单体的影响,该荧光聚合物可以对电化学和酸碱改变做出响应,并在相应刺激下诱导产生两种不同的拟轮烷单体作为聚合物单体。
     第四章利用非共价作用控制具有特定性能的分子的自组装是分子器件纳米加工的主要驱动力。独立单体的功能基团不仅可以为超分子聚合物的构建提供连接体,而且可以将优良的性能引入到超分子聚合物中。例如,光响应单体分子为所得超分子聚合物结构变化和形成／解离提供了光控途径。手性单体可以将手性引入到超分子聚合物中,从而形成手性超分子结构,展现出有趣的手性光学性能。我们提出合成双-对-磺化杯[4]芳烃与基于α-环糊精的包含手性1,1’-联萘和光响应偶氮苯单元的拟[3]轮烷,在主客体识别作用下,组装形成光驱动线形手性超分子聚合物。该超分子聚合物在非共价主客体作用驱动下的识别作用通过一维核磁谱图确认,其光响应性能通过紫外可见吸收光谱、扫描电子显微镜(SEM)、透射电子显微镜(TEM)测试表征。超分子聚合物的手性通过圆二色光谱确认。手性聚合物在光驱动下产生的显著形态变化也通过TEM和SEM观察。更有趣的是,长度为数百纳米至微米的水中动力学自组装的光驱动的单一线形手性超分子聚合物,在Cryo-TEM测试中观察到其自然态。同时,测试中观察到的单一超分子聚合物的长度也表明,杯芳烃与拟轮烷间的主客体复合在水中保持稳定。更重要的是,分子模拟也充分验证了这一有趣的光响应超分子聚合物的结构。
     第五章环糊精(CD)、葫芦脲(CB)和杯芳烃,作为三种不同的主体大环化合物,分别提供了特殊结构及迥异的超分子包结性能,被广泛用于轮烷和拟轮烷的构建中。在最近几年中,大量包含两个或多个大环组分于一个互锁体系(如轮烷低聚物)的轮烷和拟轮烷被研究和报道。然而,只有少量轮烷和拟轮烷体系包含两个或多个不同的主体大环。众所周知,水溶液中,α-CD可以包结乙烯吡啶和偶氮吡啶单元,CB[7]和SC4倾向于以高包结系数(约105L/mo1)包结双阳离子联吡啶单元。哑铃分子与α-CD, CB[7], SC4以不同模式包结,我们利用这个性质构建了拟[2]轮烷R,拟[3]轮烷R1和R2,拟[4]轮烷R1’,R2’和R3。这三种拟[4]轮烷一定程度上也可以看做是基于α-CD的轮烷,其两端被CB[7]和SC4以高常数包结,从而可以防止α-CD滑离R0。特别要指出的是拟[4]轮烷R3,它包含一个α-CD与偶氮苯单元包结的部分,和另外两个CB[7],SC4与4,4’-联吡啶单元分别包结的部分。据我们所知,这是将三种不同大环(α-CD、CB[7]、SC4)同时引入一个超分子拟轮烷体系研究的首例。这些复杂超分子体系的构建为多功能分子器件的发展建立了新的基础。
     第六章设计与合成新型功能性化合物是制造未来先进功能材料的基础,而器件化则是将化合物投入实际应用的关键步骤。我们组在构建溶液体系功能性分子机器方面做了大量工作,但是能够固态化和器件化的则很少。因此,将分子机器引入在液晶和器件化领域的研究,将很大程度推动分子机器及功能液晶材料双向领域的发展,攻克新的科研难题,同时可能在超分子器件化及功能液晶材料应用方面创造出新的科研领域。我们设计合成了多种液晶掺杂体分子机器和环状手性体系,对其进行了掺杂液晶实验和响应旋光改变能力测试。
     第七章结论
Supramolecular polymers are defined as polymeric arrays of monomeric units that are brought together by reversible and highly directional secondary interactions, resulting in polymeric properties in dilute and concentrated solutions, as well as in the bulk. The monomeric units of the supramolecular polymers themselves do not possess a repetition of chemical fragments. The directionality and strength of the supramolecular bonding are important features of systems that can be regarded as polymers and that behave according to well-established theories of polymer physics.
     Supramolecular polymers, the combination of supramolecular chemistry and polymer science, can be defined as polymeric systems that extend beyond the molecule and utilize noncovalent interactions to direct their assembly, to control their conformations, and/or to define their behavior. Due to the reversibility of noncovalent interactions, these materials are capable of undergoing self-healing and adaptation processes, which afford supramolecular polymers a major advantage over conventional, covalently bonded polymers. The responsiveness to external stimuli may further provide a range of potential applications such as smart/adaptive materials and devices.
     In Chapter one, the progress of fuctional supramolecular pseudorotaxane polymer was reviewed. It demonstrated the definition of supramolecular polymer, types of stimuli responsive supramolecular polymer and their promising application. The emphasis of review was paid to molecular machines based supramolecular polymer, and systematically introduced various functional supramolecular polymer based on cyclodextrin, calixarene, cucurbit and other macrocyclic system.
     In Chapter two, the host-guest interaction based on calixarene derivatives are relatively less explored in supramolecular polymers, while crown ethers and cyclodextrins as relatively common host monomer units has been studied systematically. We report here the formation of a novel fluorescent supramolecular polymer formed from two complimentary monomers which contain p-sulfonatocalix[4]arene based homoditopic receptor and the viologen and dimethylamino connectors decorated with a fluorophore. The fluorescent polymer can response to both electrochemical redox and pH variance, engendering two kinds of pseudorotaxanes formed as unimers induced by respective stimuli. Despite some calixarene-based supramolecular polymers in previous and more recent works, no such reversibly controlled electrochemical and pH dual-responsive fluorescent system has been reported before. Moreover, it novelly involves two disparate pseudorotaxanes as unimers in the reversible assembly/disassembly process of supramolecular polymer. The assembly/disassembly process of polymer, reversibly controlled by electrochemical and protonation/deprotonation can be conveniently addressed by fluorescence emission variance and induced circular dichroism (ICD) signals.
     In Chapter three, the charge-transfer (CT) interactions and donor-acceptor interactions between π-systems have become important classes of non-covalent interactions, and been greatly exploited in the design and synthesis of self-organizing systems. The organization of alternating electron-rich and electron-deficient units has also been employed to create novel macromolecules with folded structures. The properties of a supramolecular polymer can be adjusted by modulating the properties of its relevant monomers. Combining the well-known properties of macromolecule with supramolecular polymer has an enormous potential to alter the properties of polymer in a controlled way. By involving different pseudorotaxanes in reversible stimulus-responsive supramolecular polymer, we can enormously open the way of exploring potentially applicable aspects of supramolecular polymers as data memories and logic functions in nanoscale. We report here the formation of a novel fluorescent and high polymerized supramolecular polymer based on host-stabilized CT interactions between a viologen dication connector and a cyano-stilbene fluorophore decorated with dimethylamino portion. The fluorescent polymer can be formed by bringing the monomer's donor and acceptor units of close proximity inside the CB[8] cavity, resulting in a stable intermolecular CT complex stabilized by CB[8]. At the same time, because that the properties of the polymer are affected by the relevant monomers, the polymer can response to both electrochemical redox and pH variance, with two kinds of pseudorotaxanes formed as monomers when induced by respective stimuli.
     In Chapter four, the ability to control molecular self-assembly with tailored properties by non-covalent interactions is a major driving force in the bottom-up nanofabrication of molecular devices. Photoresponsive monomer molecules can provide a path to remotely control the resulting supramolecular polymer morphology or formation by light. Chiral monomers can impart chirality into the supramolecular polymers to form chiral suprastructures which may exhibit some fascinating chirooptical properties. Light-driven linear chiral supramolecular polymer was constructed in water by host-guest molecular recognition between bis-p-sulfonatocalix[4]arenes and the α-cyclodextrin based pseudo[3]rotaxane containing axially chiral1,1'-binaphthyl and photoresponsive azobenzene moieties. The successful supramolecular polymerization by non-covalent host-guest molecular recognition was confirmed by1H NMR, and its photoresponsive behavior was investigated by UV-vis absorption spectra, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) measurements. The chirality of this supramolecular polymer was confirmed by circular dichroism spectra. The dramatic morphology change of this chiral polymer driven by light was observed in TEM and SEM images. More interestingly, the dynamically self-assembled, light-driven single linear helical supramolecular polymer with a length of hundreds of nanometers to micrometers in water was directly observed in its native state using Cryo-TEM measurements.
     In Chapter five, cyclodextrin (CD), cucurbituril (CB) and calixarene, as three different host macrocycle compounds provided with special structures and disparate supramolecular inclusion performances respectively, have been extensively employed to construct rotaxanes and pseudorotaxanes. Many rotaxanes or pseudorotaxanes incorporating two or more components in one interlocked system (either rotaxane oligomer or not) have been constructed in recent years. However, there were only a few rotaxanes or pseudorotaxanes incorporating two or more different host macrocycles in one system. The very known phenomena have been reported that a-CD can encircle on such moieties as stilbenzene and azobenzene in aqueous solution, CB[7] and SC4prefers to bind4,4'-bipyridinium (viologen) dication units with very high association constants. Then combining the dumbbell with a-CD, CB[7] and SC4in various combination modes, we constructed the pseudo[2]rotaxane R, pseudo[3]rotaxanes R1and R2, pseudo[4]rotaxanes R1', R2'and R3. The three pseudo[4]rotaxanes could be also regarded as a-CD based rotaxanes to some extent because its two end parts, included by CB[7] or SC4with very high association constants, could be used to stop a-CD slipping away from RO. In particular, the pseudo [4]rotaxane R3consists of one inclusion part between a-CD and the azobenzene moiety and another two inclusion sites between CB[7], SC4and4,4-bipyridinium units respectively. As far as we know, it is the first example that the three hetero-macrocycle (a-CD, CB[7] and SC4) host are incorporated in one supramolecular pseudorotaxane system. The constructions of these complicated supramolecular systems may set up new basis for exploiting future molecular devices with multiple functions.
     In Chapter six, synthetic chemistry plays a key role in the advancement of material sciences and life sciences, and its key point is to utilize those materials into practice is the process of mechanization. Our group has done a lot of work on kinds of functional molecular machines in solutions, while rare in solid and mechanization. So it is necessary for us to connect our abundant synthesizing experiences in molecular machine and the research in liquid crystal material, to improve the development of both fields and capture some intractable scientific problems and create new fields in the mechanization of supramolecular system and application of functional liquid crystal materials. We designed and sythesised kinds of liquid crystal dopant material based on molecular machine and cyclic chiral system, and tested its HTP by dopanting them in liquid crystal.
     In Chapter seven is the conclusion.

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