论文总字数：21632字

摘 要

超分子配合物的自组装早在2003年由Jonathan R. Nitschke课题组提出，该类型反应是在金属离子的模板作用下，基于胺醛缩合形成亚胺配位的一类高效反应，采取高对称性的前体有利于形成结构易于预测和表征的超分子配合物，在分子识别与分离、化学传感器和专一特定催化等前沿领域均有重大应用价值。

均三嗪多胺前体具有对称性高，配位拓展能力强的显著优点。本文合成了三对氨基苯基均三嗪（I），并研究了其与醛类、金属离子在乙腈溶液中的自组装，通过核磁共振和质谱技术对产物的结构进行了推测，并对客体分子的容纳作用进行了初步研究。

三对氨基苯基均三嗪（I）是以对氨基苯甲腈和三氟甲磺酸为原料，在氮气保护的碱性条件下合成的。前体I 分散在无水乙腈中，加入三氟甲磺酸亚铁以及吡啶-2-甲醛，以3：2：6的配比进行反应，在氮气保护下，于55℃搅拌，体系逐渐变成紫红色澄清液。反应12h后，过滤。向澄清的紫红色滤液加入乙醚洗涤，得到紫红色产物。前体I分散在无水乙腈中，加入三氟甲磺酸锌以及吡啶-2-甲醛，以3：2：6的比例于55℃下搅拌，体系逐渐变澄清。反应12h后，过滤。向澄清的淡黄色滤液加入2-3ml乙醚，有大量紫色固体析出。过滤，得到固体。用乙醚洗2-3遍，烘干。得到黄色固体。通过核磁证实两种自组装产物中亚胺配体的生成以及结构的高度对称性，用电喷雾质谱的手段进一步验证了这两种超分子配合物可能具有相似的螺旋体构造。通过ArgusLab模拟了螺旋体的模型，在螺旋体结构中，三个均三嗪前体模块（I）与六个吡啶醛分子形成了三个相同的配体（L），每个前体形成了两个亚胺配位点与两个Fe（II）或Zn（II）离子进行作用，最终形成螺旋结构Fe₂L₃或Zn₂L₃，而前体中没有发生胺醛缩合的氨基远离金属配位中心，伸展向外部空间。

选择了一系列平面芳环共轭分子作为客体，通过主体或客体中各氢原子位移值的变化，对Fe₂L₃和Zn₂L₃进行主客体作用考察。研究表明，Fe₂L₃与客体结合时表现出结合能力各异，其中和芘形成了测试中最匹配的主客体关系，一个Fe₂L₃螺旋体分子的每一个三嗪环部位可以与2个平面型芘分子以π-π堆积方式形成超分子作用，即Fe₂L₃螺旋体与芘作用的比例为1:6。而Zn的螺旋体配合物对各种测试客体作用相对不明显。

关键词：超分子配合物 均三嗪多胺前体 自组装 无机螺旋体 主客体化学

Abstract

The concept of “Metallosupramolecular complex” and its ability to self-assemble had been proposed by Jonathan R. Nitschke in 2003,which was reacted in the template effect of metal ions, based on a kind of high efficiency reactions, amine-aldehyde condensation, to form imine ligand, adopting high symmetry precursor is beneficial to form metallosupramolecular complex with easily predicted structure and characterization.

The precursor of s-triazine , showing high symmetry and good ability to coordinate. This passage is focused on triamine phenyl triazine （I）_,which self-assemble with aldeydes and metal ions, in the template effect of acetonitrile. And using EMI-MS and ¹H NMR to speculate and verify structure , explore its’ shape of coordination compound, and ability to accommodate guest.

The precursor（I） was a synthesis of amino benzonitrile and triflurometanesulfnoic acid, under the basic condition and the protection of nitrogen. It was dissolved in the anhydrous nitrile(Emulsion), added into Iron(II) trifluoromethanesulfonate and pyridine-2-Carboxaldehyde(3:2:6) ,under the protection of nitrogen and stirred at 55℃, the solution changed into prunus state. After 12h, filtrated it and added into diethyl ether(2-3mL) to wash repeatedly, generating prunus solid. The precursor, I, it was dissolved in the anhydrous nitrile(Emulsion), added into zinc trifluoromethanesulfonate and pyridine-2-Carboxaldehyde(3:2:6), stirred at 55℃ to get transparent solution. After 12h, filtrated it and added into diethyl ether(2-3mL) to wash repeatedly, generating faint yellow solid. The formation of imine and high symmetry of self-assembled products could be verified by 1H NMR, above this, by ESI-MS, we could certify that this two metallosupramolecular shared similar conformation of helicate. Simulated calculation by Arguslab reveals that, in the conformation of this two helicate, three molecules of s-triazine and six molecules of pyridine aldehydes were coordinated by the two(top and below) iron(II) ions or zinc iron, it formed three equal ligands(L). Each precursor would donate two amine groups to coordinate with nitrogen and iron(II) ions on the pyridine ring to form imine, finally, it would formed into helicate Fe₂L₃ and Zn₂L₃ , and the rest unreacted amine groups would expose outside away from metal coordination center.

We had selected a series of plane aromatic conjugated molecules, using changes of each 1H shift in the guest or host to inspect the host-guest interactions. The research revealed that when Fe₂L₃ combined with diverse guests, it showed different condition, the optimal matching one was pyrene. Each triazine ring of the helicate could using π-π stack to react with two plane pyrene, which means that the reacting proportion of helicate and pyrene is 1:6. When it came to Zn, its host showed bad ability to combine with guest.

Key words: supramolecular complex； multi-amine triazine; self-assemble; helicates; host-guest chemistry

目录

摘要-------------------------------------------------------------------------------------------------------------1

Abstract--------------------------------------------------------------------------------------------------------1

1. 文献综述--------------------------------------------------------------------------------------------1

1.1 概述------------------------------------------------------------------------------------------------------1

1.2 合成方法------------------------------------------------------------------------------------------------4

1.3 发展概况------------------------------------------------------------------------------------------------6

1.4 应用前景------------------------------------------------------------------------------------------------6

1.5 研究目的------------------------------------------------------------------------------------------------7

1. 实验部分--------------------------------------------------------------------------------------------8

2.1仪器与试剂----------------------------------------------------------------------------------------------8

2.1.1实验仪器--------------------------------------------------------------------------------------------8

2.1.2实验试剂--------------------------------------------------------------------------------------------8

2.1.3测试仪器--------------------------------------------------------------------------------------------9

2.2三对氨基苯基均三嗪（I）的合成 ----------------------------------------------------------------9

2.3超分子配合物的自组装-------------------------------------------------------------------------------9

1. 结果与讨论--------- ------------------------------------------------------------------------------12

3.1三对氨基苯基均三嗪（I）的谱图解析----------------------------------------------------------12

3.2 Fe₂L₃螺旋体结构验证-------------------------------------------------------------------------------12

3.2.1 Fe₂L₃螺旋体氨基—H变化探索---------------------------------------------------------------14

3.2.2 Fe₂L₃螺旋体分子计算模拟--------------------------------------------------------------------15

3.2.3 Fe₂L₃主客体研究--------------------------------------------------------------------------------16

3.3 Zn₂L₃螺旋体的结构验证------------------------------------------------------------------------------21

3.3.1 Zn₂L₃螺旋体分子与客体分子的主客体研究---------------------------------------------------22

1. 结论与展望----------------------------------------------------------------------------------------24

4.1三对氨基苯基均三嗪合成的结论------------------------------------------------------------------24

4.2 Fe₂L₃螺旋体的总结----------------------------------------------------------------------------------24

4.3 Zn₂L₃螺旋体的总结----------------------------------------------------------------------------------24

4.4展望------------------------------------------------------------------------------------------------------24

参考文献------------------------------------------------------------------------------------------------------25

致谢------------------------------------------------------------------------------------------------------------26

1. 文献综述

1.1概述

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