论文总字数：23680字

摘 要

主客体化学是超分子化学的一个重要范畴，是研究主客体分子通过分子间弱相互作用力形成组装体的科学。到目前为止，报道的主体大环分子有第一代冠醚、第二代环糊精、第三代杯芳烃、第四代葫芦脲和第五代柱芳烃。其中，柱芳烃作为新一代的超分子主体大环分子，因为具备优异的对称性和刚性结构，有进行功能化修饰和优良的空腔包结能力，所以备受研究者的青睐。

本文以芘为原料通过甲酰基化反应，与丁二胺通过还原胺化得到含二胺结构的芘的荧光染料；然后以对苯二甲醚和对多聚甲醛为试验原材料，BF₃为催化剂，合成二甲氧基柱[5]。对二甲氧基柱[5]和BBr₃在CHCl₃中在N₂保护下反应72h，生成全羟基柱[5]。全羟基柱[5]和ClCH₃COOC₂H₅在N₂保护下加入K₂CO₃中和生成全乙氧基羰甲氧基柱[5]。全乙氧基羰甲氧基柱[5]在强碱溶液中经过24h回流反应后，再调节反应溶液的pH值， 得到全羧酸钠盐柱[5]芳烃。含芘荧光染料与全羧酸钠盐的柱[5]芳烃进行包结，通过荧光滴定D/L-苯丙氨酸（D-1/L-1）、D/L-苯丙氨醇（D-2/L-2）和D/L-缬氨醇（D-3/L-3），能表现出不同的荧光响应，从而实现识别手性对映体的目标。

关键词：柱芳烃 含芘荧光染料 主-客体化学 组装 识别

Construction and Application of Pyrene-containing Fluorescent Dyes ⊂WP [5]

Abstract

Host-guest chemistry is an important field of supramolecular chemistry. It is the science of studying the assembly of host and guest molecules through

weak interaction forces between molecules (such as stacking, hydrogen bonding,dipole-dipole,etc.). So far, the main macrocyclic molecules reported are crown ether, cyclodextrin, calixarene,cucurbituril, and pillarene. Among them, pillarenes, as the fifth-generation hosts, are highly favored by researchers due to their high symmetry and rigid structure, functional modification and excellent cavity inclusion ability.

Firstly, pyrene is used as a raw material through formylation reaction, and reductive amination with butylenediamine and hexamethylenediamine is used to obtain a fluorescent dye containing a diamine structure of pyrene. Secondly, para-methoxybenzene and paraformaldehyde are used as experimental raw materials, BF₃ as a catalyst, a dimethoxy pillar[5]arene was synthesized. The dimethoxy pillar[5]arene and BBr₃ were reacted in CHCl₃ as solvent under N₂ protection for 72h to generate a full hydroxyl pillar[5]arene. Thirdly, The full hydroxyl pillar[5]arene and ClCH₃COOC₂H₅ are added to K₂CO₃ under the protection of N₂ and neutralized to form a perethoxycarbonyl methoxy pillar[5]arene. The perethoxycarbonylmethoxy pillar[5]arene was refluxed in a strong alkaline solution for 24 hours, and the pH of the reaction solution was adjusted to obtain pillar[5]arene of percarboxylic acid sodium salt. At last, the fluorescent dye containing a diamine structure of pyrene and pillar[5]arene of percarboxylic acid sodium salt was subjected to fluorescence titration.

The inclusion behavior, proportion and inclusion constant were verified by nuclear magnetic method and fluorescence results. The assembly formed after encapsulation was further titrated with fumaric acid / maleic acid (FA / MA), D / L-phenylalanine (D-1 / L-1), D / L-benzene Alaninol (D-2 / L-2) and D / L-valinol (D-3 / L-3) ,which can show different fluorescence responses to achieve the recognition of cis-trans and chiral enantiomers purpose.

Key words: Pillararene;Pyrene-containing fluorescent dye;Host-guest chemistry; Assembly;Recognization

目 录

含芘荧光染料⊂WP[5]的构建及应用 I

摘 要 I

Abstract II

第一章 文献综述 1

1.1引言 1

1.2主客体化学 2

1.3柱芳烃的主客体化学 4

1.3.1柱芳烃的合成研究 4

1.3.2 水溶性柱芳烃的合成研究及应用发展 8

1.4客体荧光分子概述 10

1.4.1荧光产生原理 10

1.4.2 荧光分子探针识别机理 11

1.4.3 荧光分子识别 13

1.5本课题研究内容以及意义 16

第二章 实验部分 18

2.1 实验投料及试剂 18

2.2实验仪器 18

2.3实验原理 19

2.4实验方法 19

2.4.1含芘荧光染料的合成 19

2.4.2 WP[5]的合成 20

第三章 含芘荧光染料⊂WP[5]的构建及识别研究 22

3.1 试剂及仪器 22

3.2 2a⊂WP[5]的荧光滴定和紫外滴定特性 22

3.3 2a⊂WP[5]对D/L-苯丙氨酸的识别 23

3.4 2a⊂WP[5]对D/L-苯丙氨醇的识别 24

3.5 2a⊂WP[5]对D/L-缬氨酸的识别 24

3.6结果与讨论 25

3.7小结 25

第四章 结论与展望 27

4.1结论 27

4.2展望 27

参考文献 28

致 谢 33

文献综述

1.1引言

超分子化学起源于美国的C. J. Pedersen^[1]在60年代发现了冠醚，随后在他和J. M. Lehn，D. J. Cram两位科学家对冠醚进一步深入研究。最先定义超分子化学的是，法国著名大学的莱恩教授^[2]。传统意义上来讲，超分子是指几个成分：一个受体和一个或者多个底物，遵从内装的构造方案实现分子间缔合从而形成了寡聚分子物种，这样的过程在分子识别原理的基础上实现。现在的超分子化学研究显示，分子之间发生了弱相互作用，从而能够组成复杂有序，且具备特定功能的化学体系，使得超分子有序体得以形成，是超分子化学的重要探究部分。

超分子化学发展的重点是大环主体分子的设计。主体分子通常富电子，与客体分子发生相互作用。科学家们己经合成了冠醚^[3]、环糊精^[4]、杯芳烃^[5]、葫芦脲^[6]以及柱芳烃^[7]（图1-1）。这些大环主体分子的空腔构造性质都大不相同，各有特色，能够和各种客体分子组装形成特定的超分子结构，它们在众多领域广泛运用^[8]。

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