【作者】 张轶群；

【导师】 刘鸣华；

【作者基本信息】 中国科学院研究生院（化学研究所） ， 物理化学， 2009， 博士

【摘要】 手性超分子功能组装体在性能调控方面具有多样、灵活的特点,在分子识别、手性催化、材料科学尤其是纳米科学领域有良好应用前景,是手性学科发展的一个重要方向。手性超分子材料的性能一方面取决于分子本身,另一方面取决于分子的堆积方式。相应地,如何在分子水平上设计构筑单元,在超分子层次上控制构筑基元的排列方式,进而有效地控制材料的性能在有机纳米材料领域具有重要的意义。本论文选择卟啉、偶氮苯与蒽衍生物作为模型分子,通过界面组装可控地制备了手性超分子组装体,探讨了分子间相互作用力的强度、分子构型和分子排列方式对手性超分子材料的光学和电学性质的影响。首先,发展了一种从非手性卟啉制备手性超分子组装体的普适性方法,对其他大环共轭分子的组装具有指导意义,拓展了适用于通过界面上对称性打破方法制备手性超分子材料的构筑基元的范围。其次,对超分子手性产生机理进行了探究。选择了卟啉和偶氮苯两种响应性功能分子,分别通过改变抗衡离子种类和光致异构,对组装体的超分子手性进行调控。该研究证明了强度合适的分子间相互作用和平面型分子构型对手性超分子组装体的构筑至关重要。构筑基元的普遍化和对超分子手性机理的深入理解为手性超分子材料的功能化奠定了基础。在上述研究的基础上,我们选择了一种蒽衍生物分子,通过调节界面组装过程的表面压,在分子水平上控制构筑基元的排列方式和调控分子间π-π交叠程度,进而可控地制备了具有不同形貌、超分子手性特征及光电性质的有机纳米材料。该研究表明,有机构筑基元的界面组装为控制纳米材料的形貌及光电性质提供了一种简便的方法,同时也表明,圆二色光谱不仅可以用来表征组装体的手性,也可用来关联功能共轭分子之间的相互作用。更多还原

【Abstract】 Chiral supramolecular functional assemblies with great chemical structure variety and property tunability, are of crucial importance in the field of molecular recognition, asymmetric catalysis, material sciences, and especially nanotechnology and nanosciences. Chiral supramolecular functional materials play an important role in chiral subject. The properties of chiral supramolecular materials are not only determined by the molecules themselves, but also depend on the molecular packing statues. To control the function of materials by designing the building blocks at molecular level and regulating packing manners of building blocks at supramolecular level is essential and meaningful in the field of organic nanomaterials.In this dissertation, we employed porphyrin, azobenzene and anthracene derivatives as model molecules, and constructed chiral supramolecular assemblies which are controllable by interfacial organization. We discussed the effect of intermolecular interaction, molecular configuration, and packing statues of molecules on the optical and electrical properties of chiral supramolecular assemblies.Firstly, we developed a general method for constructing chiral supramolecular assemblies from achiral porphyrins, which are of guiding significance to other conjugated macrocyclic molecules, and expanded the scope of building blocks which are suitable for constructing chiral supramolecular materials through symmetry breaking at interface.Secondly, we explored the mechanism of suprmolecular chirogenesis. We used two responsive functional molecules, porphyrin and azobenzene, and controlled the supramolecular chirality of assemblies by changing counterion and photoisomerization, respectively. Our investigation confirmed that proper strength of intermolecular interaction and planar molecular configuration are essential to the formation of chiral supramolecular assemblies.The expansion of scope of building blocks and deeper insight into the mechanism of supramolecular chirogenesis provide foundation of functionalizing chiral supramolecular materials.Based on the research mentioned above, we selected an anthracene derivative and adjusted the surface pressure during the interfacial organization process to control the packing manners of building blocks and the degree of intermolecularπ-πoverlapping, and further controllably fabricated organic nanomaterials exhibiting distinct morphology, supramolecular chirality and photoswitching properties. Our research indicated that, interfacial organization of organic building blocks provided a facile way to control the morphology and photoelectric properties, and also suggested that CD spectrum can be apply not only to characterize the chirality of assemblies, but also to correlate the interactions between conjugated functional molecules.更多还原