论文总字数：37834字

摘 要

近年来，固体有机发光材料由于在光子及光电子器件方面具有很强的应用潜力，其设计合成日益受到人们的关注。但是，传统的固体发光材料由于聚集导致荧光猝灭(aggregation caused quenching，ACQ )的现象，在应用时需要使用物理或者化学手段来阻止荧光分子间的聚集，从而显著地提高了发光材料的应用成本。因此，具有聚集诱导发光(aggregation-induced emission，AIE)效应的材料成为了当前发光材料的新星。自2001年唐本忠课题组报导具有AIE特性的分子以来，大量的具有AIE特性的光电材料被设计、合成并且应用到光电功能材料领域中。其中，过渡金属配合物(transition metal complexes，TMC)，特别是Ir(III)配合物，因其发射效率高、激发态寿命较长、光热稳定性以及发光波长可调等优点，被广泛地应用于化学传感器、生物探针、光电化学电池（Photoelectrochemistry Cell,PEC）以及有机发光二极管(Organic Light-Emitting Diode，OLED)等领域，逐渐成为新型AIE功能材料的研究热点。

本文以Ir(Ⅲ)为金属中心，以2-(2,3,4,5-四氟苯基)吡啶为环金属配体，以3,6-二-叔丁基-9-(4-(4,5-二甲基-2-(吡啶-2-基)-1H-咪唑-1-基)丁基)-9H-咔唑作为辅助配体，设计合成[(tfppy)₂Ir(L₂)] (PF₆^-)型阳离子铱配合物。通过核磁共振氢谱、质谱对其结构进行了表征，确认其结构与预期相符。在此基础上，通过紫外吸收光谱、荧光发射光谱、透射电镜、动态光散射等技术对配合物的光物理性质和AIE性质进行了系统地探究。基于该配合物良好的AIE性质，对其进行了指纹识别的应用拓展。研究结果表明，该目标配合物在指纹识别领域具有良好的应用前景。

关键词：聚集诱导发光 磷光材料 铱配合物 合成 指纹识别

Synthesis and Application of Iridium Complexes with Aggregation-induced Emission Property

Abstract

In recent years, solid organic luminescent materials due to a potential strong application in photonics and optoelectronic devices, its design and synthesis of the growing concern. However, due to aggregation caused by fluorescence quenching (aggregation causes quenching, ACQ) phenomenon of the traditional solid luminescent material, the use of physical or chemical means is required to prevent aggregation of fluorescent molecules during application, thereby significantly increasing the application cost of the luminescent material. Thus, a material with an aggregation-induced emission (AIE) effect becomes a star of the current luminescent material. Since 2001, Tang benzhong's group reported that molecules with AIE characteristics, a large number of optoelectronic materials with AIE characteristics are designed, synthesized and applied to the field of optoelectronic functional materials. Among them, transition metal complexes (TMCs), especially Ir (III) complexes, are widely used in chemical sensors, biological probes, photoelectrochemistry cells (PECs), because of their high emission efficiency, longer lifetime, thermal stability and light emission wavelengths, organic light-emitting diodes (OLED) and other fields, have gradually become a new hotspot of AIE functional materials research.

In this paper, Ir (Ⅲ) was used as the metal center, with 2- (2,3,4,5-tetrafluorophenyl) pyridine as the ring metal ligand, with 3,6-di-tert-butyl- (4,5-dimethyl-2-(pyridin-2-yl)-1H-imidazol-1-yl) butyl) -9H-carbazole as an auxiliary ligand, (tfppy)₂Ir(L₂)] (PF₆^-) cationic iridium complexes were designed and synthesized. The structure was characterized by nuclear magnetic resonance spectroscopy and mass spectrometry, and the structure was confirmed to the expectation. On the basis of this, the photophysical properties and AIE properties of the complexes were systematically investigated by UV absorption spectroscopy, fluorescence emission spectroscopy, transmission electron microscopy and dynamic light scattering. Based on the good AIE properties of the complex, the application of fingerprint identification was extended. The results show that the target complex has a good application prospect in the field of fingerprint recognition.

Key words: AIE; Phosphorescent material; Iridium complexes; synthesis; Fingerprint recognition

目 录

摘 要 I

Abstract II

第一章 文献综述 2

1.1 引言 2

1.2 聚集诱导发光(AIE)机理 3

1.2.1 分子内自旋受限（RIR） 3

1.2.2 分子内共平面 5

1.2.3 形成J-聚集体 5

1.2.4 非紧密堆积 6

1.3 铱配合物的聚集诱导磷光发射 7

1.3.1 铱配合物的发光原理 7

1.3.2 聚集诱导磷光发射铱配合物的研究进展 9

1.4 AIE功能材料的应用 10

1.4.1 AIE分子在指纹识别方面的应用 10

1.4.2 AIE分子在信息加密方面的应用 12

1.5 本课题的研究思路和方法 13

第二章 金属有机铱(Ⅲ)配合物的合成与结构表征 15

2.1 引言 15

2.2 实验部分 16

2.2.1 主要试剂 16

2.2.2 主要仪器 16

2.2.3 环金属配体和铱(Ⅲ)配合物的合成 17

2.3 结果与讨论 20

2.4本章小结 21

第三章 铱(III)配合物的光物理性质及聚集诱导发光性质的研究 22

3.1引言 22

3.2 实验部分 22

3.2.1主要仪器 22

3.2.2 实验过程 23

3.3 结果与讨论 24

3.3.1光物理性质测试与表征 24

3.3.3 聚集诱导发光性质的研究 26

3.4 小结 28

第四章 [(tfppy)₂Ir(L2)] PF₆⁻在指纹识别方面的应用探究 30

4.1 引言 30

4.2 实验部分 30

4.3 结果与讨论 31

4.4 小结 32

第五章 结论与展望 34

5.1结论 34

5.2展望 34

参考文献 36

附 录 41

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