【作者】 李志强；

【导师】 刘育；

【作者基本信息】 南开大学 ， 有机化学， 2014， 博士

【摘要】 作为超分子化学发展过程中的第二代大环主体化合物,基于环糊精的分子识别和分子自组装在超分子化学领域占有举足轻重的地位。另一方面,由于其独特的光电特性和电子传输行为,基于卟啉和酞菁的研究由来已久并且广泛深入。但这其中,大部分工作集中在卟啉或者酞菁的单独研究和卟啉-酞菁共价连接体的研究,基于卟啉-酞菁量非共价自组装的研究尚处于初步探索阶段,而超分子主客体化学在构筑非共价可逆可控自组装方面有着独特的优势。在本论文工作中,我们充分利用全甲基化环糊精对阴离子卟啉的强键合行为,以环糊精为媒介和连接剂,构筑了基于卟啉-酞菁的高级有序纳米组装体,以期达到对其光物理性质的有效放大。并研究了形成的高级有序组装体在捕获富勒烯、光刺激响应可逆调控,作为催化剂平台以及在制备金属纳米线中的模板效应等方面的应用。具体研究内容如下：(1)我们设计并合成了酞菁修饰环糊精,采用多价键合的理念利用环糊精与卟啉分子的强键合构筑了线状纳米超分子组装体。在该过程中,卟啉为给体,酞菁为受体,可实现高效的荧光共振能量转移。更加有趣的是,在该线状纳米组装体中,存在由卟啉和酞菁分子共同组成的纳米笼,该纳米笼可在水中有效捕获富勒烯分子,这是首次报道利用两种不同的大π化合物协同富集富勒烯。(2)我们利用卟啉偶氮苯衍生物与酞菁修饰环糊精构筑了球形纳米组装体,在加入交联剂后可以将较小的组装体进一步交联形成较大尺度的球形组装体,我们可以通过紫外光刺激来控制偶氮苯基团的顺反异构,进一步实现了对两种组装结构的可逆调控。(3)我们利用酞菁桥联甲基化环糊精与两亲性卟啉分子通过超分子自组装构筑了一种新颖的超分子有机纳米管。更加有意义的是,将二价钯离子(Pd2+)负载到纳米管表面后,在室温纯水环境中,该纳米管对Suzuki-Miyaura偶联反应展示出了非常高效的催化活性。(4)我们利用酞菁桥联甲基化环糊精与两亲性卟啉分子通过超分子自组装构筑了一种新颖的超分子有机纳米管。该纳米管可作为金属银纳米线的合成模板,用于合成高纵横比尺寸均匀的银纳米线,由于超分子组装体的可逆性,该管道状模板可往复利用。更多还原

【Abstract】 cyclodextrins (CDs), a class of cyclic oligosaccharides with six to eight D-glucose units, are widely used as convenient and versatile building blocks in the construction of high ordered nanoarchitectures. On the other hand, the phthalocyanine-porphyrin couples have been intensively studied during the past several decades, due to their apparent advantages to form the light-harvesting arrays with high efficiency in near-IR region. Most of the Porphyrin-Phthalocyanine Conjugates are linked by covalent bond. However, Very few quantitative studies on the Porphyrin-Phthalocyanine Conjugates are based on noncovalent. Supramolecular chemistry have unique advantages in the construction of non covalent reversible and controllable self-assembly system. In the thesis, adopt a molecular recognition strategy and supramolecular nanotechnology, we construct well ordered phthalocyanine-porphyrin supramolecular architectures through the complexation of permethylated β-cyclodextrin with porphyrin. we have constructed several porphyrin-phthalocyanine conjugates Mediated by Cyclodextrin, which are summarized as follows:1. A supramolecular nanowire originated from multivalent binding was successfully constructed by the complexation of phthalocyanine-grafted cyclodextrins and sulfonated porphyrin, in which the pristine C60could be efficiently captured by the preorganized π-electronic cavitand in water.2. In this work, considering the’orthogonal’host-guest interactions of different type cyclodextrins (CDs) towards the appropriate guest molecules and photo-induced isomerization properties of azophenyl group, we herein report a novel supramolecular spherical assembly upon complexation of a porphyrin derivative bearing azophenyl moiety and phthalocyanine-grafted β-CDs. Upon addition of naphthyl bridged bis(a-CD)s, the obtained small sized spheres could be cross-linked as relatively larger spheres through the hierarchically intermolecular organization. Moreover, the large-sized spheres could be disassembled and switched to small particles as soon as trans-azobenzene was transformed to cis-isomer upon exposure to UV irradiation. 3. The extremely strong noncovalent complexation between the rigid host of phthalocyanine-bridged β-cyclodextrins and amphiphilic guest of carboxylated porphyrin is employed to construct a hollow tubular structure as supramolecular nanoreactor. The representative coupling reaction can continuously occur in the hydrophobic interlayers of tubular walls in pure water at room temperature, leading to10times higher enhancement of reaction rate without any adverse effect in catalytic activity and positive conversion.4. The extremely strong noncovalent complexation between the rigid phthalocyanine-bridged β-cyclodextrins and amphiphilic porphyrins is employed to construct a hollow tubular structure as a reusable soft template. This supramolecular tubule can be repeatedly used to guide the synthesis of uniform Ag nanowire, which exhibits the high-performance surface-enhanced Raman scattering ability with a higher enhancement factor value.更多还原