论文总字数：33142字

摘 要

智能有机发光材料能够根据外界刺激（如力、热和溶剂熏蒸等）改变其发射波长，在传感器、探针、安全和存储设备中的应用引起了研究者的广泛关注。作为智能有机发光材料的一个典型代表，有机力致变色材料是一类由机械刺激（如研磨、摩擦或挤压等）导致光学行为发生变化的有机功能材料，其在商标防伪、信息安全保护、记忆芯片以及信息存储等领域展现的极大的应用前景。

本课题以开发新型有机力致变色发光材料为目的，具有聚集诱发光性质和力致变色性能的新型vinamidinium盐（1,5-二氮杂戊二烯盐）N1和N2被设计合成出来，经核磁氢谱、碳谱、高分辨质谱对其结构进行了表征，并对其光物理性质和性能进行了研究。具体内容如下：

首先，通过水解反应、亲核加成反应合成了vinamidinium盐N1和N2，经过核磁氢谱、核磁碳谱、高分辨质谱等方法，证明所合成的化合物结构与预期目标产物结构相符。分别通过紫外-可见吸收光谱及发射光谱系统研究了其光物理性质。化合物N1和N2在300nm到450nm之间呈现较宽的吸收带，说明其共轭体系的¹π-*π跃迁混合有分子间的电荷转移（ICT）。N1和N2的溶液发射光谱中的435nm-461nm的发射可归因于¹π-*π跃迁混有分子间电荷转移。N1和N2在二甲基亚砜溶液中的溶液荧光量子产率分别为0.06和0.07。

其次，化合物N1和N2在稀溶液中不发光，但在聚集状态下均显示出增强的发光强度，这是典型的聚集诱导发光（AIE）现象。除此之外，N1和N2经研磨后展现出明显出力致荧光变色效果，在研磨熏蒸之后能可逆转变。X射线衍射图谱表明，这一现象来源于分子内堆积模式的变化。这使其在应力传感、信息存储和信息加密等领域展现出极具吸引力的潜在应用。

综上所述，本文经一步法快速合成了两个新型vinamidinium盐化合物（N1和N2）并进行了结构表征。随后，对化合物的基础光物理性质进行了研究。此外，化合物N1和N2均展现了聚集诱导发光性质和力致变色性能。研究结果可为开发新型的智能有机变色材料提供理论与实践指导。

关键词：vinamidinium盐 聚集诱导发光 力致变色 光物理性质

Study on Synthesis,Aggregation-Induced Emission and

Mechanochromic Properties of Novel Vinamidinium Salts

Abstract

Smart organic luminescent materials that are capable of switching their emission wavelength in response to external stimuli, such as mechanical force, heat, and solvent fuming, have attracted great attention toward their applications in sensors, probes, and security and storage devices. Organic mechanochromic materials is a typical smart organic luminescent materials that caused by mechanical stimuli ,such as grinding, crushing, or pressing.

With the purpose to develop novel organic mechanochromic luminescent materials, novel vinamidinium salts (1,5-diazapentadienium) N1 and N2 with aggregation-induced emission (AIE) and mechanochromic properties were designed and synthesized in this dissertation. After that, their structures were characterized and analyzed by ¹H NMR spectra, ¹³C NMR spectra and high-resolution mass spectrometry and their optical physical properties were studied.

Firstly, vinamidinium salts N1 and N2 were synthesized through hydrolysis reaction and nucleophilic addition reaction. And ¹H NMR spectra, ¹³C NMR spectra and high-resolution mass spectrometry confirmed the proposed structures. The optical physical properties of target molecule were investigated by UV-visible absorption spectroscopy and emission spectroscopy. All compounds exhibit a broad absorption band between 300nm and 450nm, indicating that the ¹π-*π transfer of the conjugated system is mixed with intermolecular charge transfer(ICT). Meanwhile, the emission of these compounds in solution at room temperature (λ_em =435-461nm) can be attributed to ¹π-*π transition mixed with intramolecular charge transfer (¹ICT) transitions. The quantum efficiency of compounds N1 and N2 in DMSO solution were 0.06 and 0.07.

Secondly, compounds N1 and N2 do not emit light in dilute solutions, but show increased luminescence intensity in their aggregation state, which indicates that these compounds exhibit aggregation-induced emission (AIE). In addition, these compounds also show obvious mechanochromic properties, which can be reversibly transformed after grinding and fuming, X-ray diffraction spectroscopy indicates that the reversible mechanochromism is ascribed to changes in the molecular packing mode. These properties make them very attractive potential applications in the fields of stress sensing, information storage and information encryption.

In summary, two novel vinamidinium salts N1 and N2 were quickly designed and synthesized by one-step method in this dissertation. Subsequently, the basic optical physical properties of the compound were studied. In addition, the compounds N1 and N2 exhibited aggregation-induced emission and mechanochromic. The research results can provide theoretical and practical guidance for the development of novel smart organic color-changing materials.

Key Words: vinamidinium salts; aggregation-induced emission; mechanochromic;

optical physical properties

目录

摘要 I

Abstract III

第一章 文献综述 1

1.1 引言 1

1.2 聚集诱导发光机理 2

1.3 无聚集诱导发光性质的有机力致变色材料研究进展 3

1.4 具有聚集诱导发光性质的有机力致变色材料研究进展 4

1.5本论文的研究目的、内容和意义 12

第二章 新型vinamidinium盐的合成与结构表征 13

2.1 前言 13

2.2 实验部分 13

2.2.1 主要试剂 13

2.2.2 仪器设备 14

2.2.3 新型vinamidinium盐的合成路线、合成步骤及结构表征 14

2.3 结果与表征 15

2.4 小结 18

第三章 新型vinamidinium盐聚集诱导发光及力致变色性质研究 19

3.1 前言 19

3.2 实验部分 19

3.2.1 仪器设备 19

3.2.2 溶液紫外-可见吸收光谱测试 20

3.2.3 溶液荧光发射光谱测试 20

3.2.4 固体粉末荧光发射光谱测试 20

3.2.5 聚集诱导发光性质测试 20

3.3 结果与讨论 21

3.3.1 紫外-可见吸收光谱 21

3.3.2 荧光发射光谱 22

3.3.3 聚集诱导发光性质 23

3.3.4 力致变色性质的研究 25

3.4 小结 27

第四章 结论与展望 28

4.1 结论 28

4.1.1 新型vinamdinium盐的合成与结构表征 28

4.1.2 新型vinamdinium盐聚集诱导发光及力致变色性质的研究 28

4.2 展望 28

参考文献 30

本科期间的成果及奖励 36

致谢 37

第一章 文献综述

1.1 引言

刺激响应性发光固体材料俗称“智能材料”^[1]，是通过多种不同机制的对一种或多种环境“触发”（例如光、热、压力、电场、pH、黏度或其他分子等）而产生光学行为变化。因此，其在柔性、可打印传感器、记录设备和安全印刷中具有广泛应用。其中，有机力致变色材料由于其易于合成、应用广泛等优点而被广泛关注。这类材料是指在外界力刺激下光学行为（如吸收、反射、荧光、磷光等）发生可逆转变的一类有机功能材料。

近十年中，各类有机力致变色材料（例如π-共轭的小分子染料、液晶、聚合物和有机金属配合物）被广泛开发^[2]。但由于其发展较晚且缺乏普适性的设计规律导致其研究及应用难以推进。因此，研究其力致变色机理，探究合成该类材料普适性的设计规律是目前的研究热点。大量报道表明，力致变色材料的刺激响应特性主要来源于分子间相互作用的改变，例如π-π堆积、J-/H-聚集及凝聚态内形成准分子等^[3],[4]。然而，由于分子聚集引起的猝灭效应（ACQ），这种力致变色材料的光致发光量子产率通常相当低，这限制了它们作为实际发光体的应用。因此，开发一类具有颜色变化明显、高聚集态荧光量子产率的新型力致变色材料对于理论研究和实际应用都至关重要。

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