【作者】 李媛；

【导师】 张志滨；

【作者基本信息】 西北大学 ， 材料化学， 2019， 硕士

【摘要】 富勒烯由于其独特的物理化学性质,在许多方面都有着广泛的应用。本文主要研究了基于蒽基团构筑的脲类受体与阴离子配位自组装的结构对于富勒烯C₆₀的结合。本文共论述了两类脲类阴离子受体,一类是基于蒽基团、三氨基乙基胺桥连的三足六脲配体;另一类是基于蒽基团、邻苯基桥连的二脲配体。全文共分为三章,第一章为绪论部分,主要论述了脲类阴离子受体的研究概况、基于阴离子配位的超分子自组装、基于金属配位的超分子组装体结合C₆₀的研究以及本文的选题目的及意义。第二章主要内容是三足六脲配体、配合物的合成及表征,以及其配合物结合C₆₀的性质研究;第三章主要内容是不同末端二脲配体、配合物的合成及表征,及其配合物结合C₆₀的性质研究。第二章和第三章实验内容如下:1.第二章主要合成了以三氨基乙基胺桥连、末端蒽取代的三足六脲受体L¹,通过单晶证明了其与磷酸根可以组装成1:1的结构（TPA）₃[（PO₄）（L¹）]（2）;通过核磁、荧光、紫外以及DFT计算研究了其配合物（TBA）₂[（SO₄）（L¹）]（1）与C₆₀之间的结合;核磁表明,配合物和C₆₀在CDCl₃溶液中,配合物的化学位移发生明显变化,说明存在相互作用;配合物的荧光发生淬灭现象表明了配合物与C₆₀之间的存在电子转移,进一步说明配合物和C₆₀之间有相互作用;荧光滴定证明了配合物与C₆₀之间可以形成2:1的结构,以及计算得到其结合常数为K_a1=（1.18±0.08）×10³ M^-1和K_a2=（6.67±0.43）×10³ M^-1;DFT计算表明了其结构信息:两个配合物与一个C₆₀分子通过π-π相互作用形成了一个胶囊结构。2.基于二脲配体L^a-d可以与硫酸根、磷酸根形成3:1的结构,与三足六脲配体L¹和磷酸根、硫酸根配位结构相似,在第二章的基础上,第三章主要合成了基于蒽取代、邻苯基桥连的二脲配体L^a-d。单晶结构证明,二脲配体可以与PO₄^3-配位形成3:1结构;核磁及质谱证明了其3:1结构;通过研究二脲配体的硫酸盐配合物与C₆₀之间的相互作用,二脲配体的硫酸盐配合物和C₆₀在CDCl₃溶液中,配合物的核磁没有发生变化,表明配合物和C₆₀之间并没有相互作用。证明了三足骨架对于结合C₆₀的重要性。更多还原

【Abstract】 Fullerenes have attracted wide attention due to both the unique physical and chemical properties,as well as the wide applications in many research fields.In this paper,the binding of fullerene C₆₀ to anthracene-based urea receptor and anion coordination self-assembly structure was studied.Two kinds of urea-based receptors are described in this thesis.One is the tren-based tripodal with anthracene receptors.The other is bis-urea receptors based on anthracene groups with different terminal substituents.This thesis is divided into three chapters.The first chapter summarizes the development of anion coordination chemistry,the literature works in urea-based anion receptors and anion coordination self-assembly,Study on the encapsulation of C₆₀ in metal-coordination-based supramolecular assemblies,which inspires the topic selection and research significance of this thesis.The second chapter is mainly about the synthesis of bis-urea receptors with different terminal substituents and the study on properties of their complexes.The third chapter is mainly about the synthesis of tripodal hexaurea receptors and the interactions of complex with C₆₀.The main experimental contents in chapter 2 and chapter 3 are as follows:1.In the second chapter,the tripodal hexaurea receptor L¹,which is composed of tren-bridging and anthracene substituents,was synthesized.The receptor L¹ with PO₄^3-to form the 1:1 complex（TPA）₃[（PO₄）（L¹）]（2）.The binding of its complex（TBA）₂[（SO₄）（L¹）]（1）to C₆₀ was studied by NMR,fluorescence,UV-vis and DFT calculation.Firstly,NMR showed that there were interactions in CDCl₃ solution,among which,the combination of complex（TBA）₂[（SO₄）（L¹）]（1）and C₆₀0 was also indicated by fluorescence and UV-vis.Job’s plot shows a 2:1 stoichiometry between complex（TBA）₂[（SO₄）（L¹）]（1）and C₆₀.And the binding constants were calculated to be（1.18±0.08）×10³ M^-1 and（6.67±0.43）×10³M^-1 for K_a1 and K_a2 by fluorescence titration.The structure information was studied by DFT calculation,which showed that two complexes and one C₆₀ molecule formed a capsule structure.2.Based on the bi-urea ligand L^a-d,a 3:1 structure can be formed with SO₄^2-and PO₄^3-,which is similar to the coordination structure of the tripodal hexa-urea ligand L¹ with PO₄^3-and SO₄^2-.In the third chapter,the bis-urea ligands L^a-d was synthesized based on anthracene substitution and o-phenyl-bridging.The single crystal structure proved that the bis-urea ligands could coordinate with PO₄^3-to form a 3:1 structure.The structure of its 3:1 is further demonstrated by NMR and MS.The interaction between C₆₀ and sulfate complex of bis-urea ligand was studied.It was found that there was no interaction between sulfate complex of bis-urea ligand and C₆₀ in CDCl₃ solution,revealing the tripodal structure plays an important role during the encapsulation of C₆₀.更多还原