Syntheses, Structure And Properties Of Supramolecular Structures Based On Triptycene Derivatives

Triptycene carboxylates and amine derivatives support to form a stable mainbody frame structure for their special rigid construction and high symmetry. The freevolume which is open in three-dimensional, made up of three benzene rings, is a idealreceptor accumulated π electron. They received extensive attention from peoplebecause of the particularity of their structure and property,and widely used in manyfields,including supramolecular chemistry, material chemistry and molecular devices,etc. Based on the particularity of triptycene`s skeleton,this thesis took triptyceneramification as construct units of supramolecular,and assembled supramolecularutilizing the interaction of hydrogen bond, π…π accumulation and coordination bond,etc,and the triptycene supramolecular compound which has particular structure andproperty was prepared.The primary research contents and results are as follows:1. Synthesis of triptycene carboxylic acid, amine derivatives basedtriptycene,and the research of their fluorescence property.Starting from origin raw materials,the optimum synthetic route chooses based onsynthesizing the synthetic method of triptycene,and the triptycene carboxylic acid andamine derivatives with rigid structure in three-dimensional were prepared,they werecharacterized by FT-IR，1H-NMR.The different grafted group for supplying electronof triptycene had different fluorescence properties, the optical property of triptycenederivatives can be characterized by fluorescence emission spectrum and ultraviolet-visible absorption spectrum,test results showed that, triptycene carboxylic acid andamine derivatives both could interact with solvent in virtue of different intermolecularforces,its fluorescence properties were enhanced,and these results provide basis forthe exploration of its solid-state construction and fluorescence properties.2. Triptycene triamine units built supramolecular compound, captured aseventeen nu-cleared water cluster.A compound with porous structure formed by self-assembly via the effect ofN…O hydrogen bond which was existed in triptycene triamine.After the analysis of structure1in the compound,we found that, the function of exoteric template playedan promoting role in the formation of water cluster.The fluorescence property andthermal stability of the crystal had been researched at the same time,and we found thecrystal had fine thermal stability and fluorescence property.3.Taking triptycene carboxylic acid as supramolecular to build units,a series ofsupramolecular compounds were synthesized.Compound2built three-dimensional structure utilizing hydrogen bond camefrom the oxygen of carboxylic acid,and the solvent molecules were padded.Compound3formed two-dimensional folded layer utilizing hydrogen bond betweencarboxylic acid and bipyridine and π accumulation,and each layer connected by theformed one-dimensional water cluster structure via the water surrounded,and thethree-dimensional network which had stable structure formed ultimately.Thehydrogen bond of carboxylic acid in compound4eliminated by special syntheticmethod,and after discussing the variation of supramolecular network,we found, atriptycene anhydride crystal growed in this condition,and the supramolecularnetwork built by π accumulation absolutely.When hydrogen bond damaged by metal,acoordination polymer5with metal-organic framework cultured, the structure analysisresult showed that the ligand of the coordination polymer formed a three-dimensionalstructure by π…π accumulation and close packing during molecules.The results ofTG and fluorescence characterization showed the compound possess excellentthermal stability and fluorescence radiation.