【作者】 王莉；

【导师】 文珂；

【作者基本信息】 华东师范大学 ， 化学生物学， 2013， 硕士

【摘要】 近年来,杯芳烃作为超分子主体化合物,已经引起了化学、晶体学、生物学以及材料学等各学科众多科学工作者的关注。由于超分子的合成过程简单、具有可调节的空腔、独特的形状和多功能识别位点,使其具有分子或离子识别功能的主客体性质及自组装功能,所以超分子主体分子的设计、合成成为研究热点。本文以三嗪苯和四联苯为结构单元设计并合成了一类三棱柱状的(杂环)杯芳烃及杯芳烃冠醚超分子主体,并对这类化合物的分子识别功能、与金属离子配位自组装形成复杂的超分子化合物等功能进行了探索。1.以2,4,6-三(4-羟基苯基)三嗪、1,3,5-三(4-甲氧基苯基)苯为结构单元,合成了三个三棱柱状杯芳烃目标化合物(化合物3.4、3.10、3.12),并利用1H-NMR、13C-NMR、高分辨质谱、红外光谱分析、元素分析及X-Ray单晶衍射等分析方法对其结构进行表征与确认,并对化合物的离子识别功能及自组装性质进行了研究,研究发现化合物3.12可以与银离子形成有机金属配合物。2.利用2,4,6-三(4-羟基苯基)三嗪与1,5-二氟-2,4二硝基苯、2,6-二氯毗嗪、2,6-二氯吡啶等卤带芳杂环进行亲核取代反应合成一系列三棱柱状杯芳烃冠醚,并利用1H-NMR、13C-NMR及高分辨质谱等分析方法对其结构进行确认,部分化合物经过X-Ray单晶衍射确定其晶体结构。由于所合成的目标化合物具有冠醚官能团,而冠醚能够捕获客体分子或碱金属离子,杯芳烃冠醚这类化合物结合了杯芳烃和冠醚的共同性质,在分子离子识别方面应该能够成为更好的超分子主体。本文共合成了11个新的大环化合物,共得到5个化合物的单晶结构和一个有机金属络合物。更多还原

【Abstract】 Calix[n]arene, as the host compound, have attracted considerable interest in the field of Chemistry, Crystallography, Biology and material science over the past years. Supramolecular not only can capture neutral molecules or other ions to form the host-guest complex, but also have strong coordination ability of metal ions due to their synthetic availability, tunable cavity structures and special conformational features. So the design and synthesis of the supramolecular host is a hotspot in ’host-guest’chemistry. In this paper, we have designed and synthesized a new kind of Trigonal Prismatic Bicyclocalixaromatics, and has done some research on the ability of their capabilities of coordination-driven self-assembly to capture neutral molecule and coordinate with metal ions forming supramolecular complexes.1. We synthesized three trigonal prismatic bicyclocalixaromatics (compound3.4,3.10,3.12) in which the1,3,5-tri(p-oxaphenyl)benzene and2,4,6-tri(p-oxaphenyl)triazine are placed in the "top" and "bottom" of the triangular prismatic structures and dinitro-dioxa-phenyl units play the role of the three pillars. All the structures were confirmed by1H-NMR,13C-NMR, HR-Mass, infrared spectroscopic methods, elementary analysis and X-Ray single crystal diffraction analysis。Through the investigating the coordination ability. We found compound3.12can coordinate with Ag+.2. We synthesized a series of trigonal pismatic Calixcrown via sequential nucleophilic aromatic substitution reactions using2,4,6-tri(p-oxaphenyl)triazine with electron deficient dihalogenated benzene or heterocycles, such as1,5-difluoro-2,4-dinitrobenzene,2,6-dichloropyrazine and2,6-dichloropyridine. All the structures were confirmed by1H-NMR,13C-NMR and HR-Mass and two of them was further confirmed by single crystal X-Ray analysis. Calixcrown, combining the features of the calixarene and crown, will be a better supramolecular host. In this paper, we synthesized eleven new Bicyclocalixaromatics derivatives and five of them was confirmed by single crystal X-Ray analysis. We also got one metal-organic compounds.更多还原