论文总字数：36656字

摘 要

刺激响应型材料是一种智能材料，可在外界刺激诱导下产生信号或目标行为，刺激手段主要包括 pH 值，电化学、金属离子、温度、压力、光等，产生的响应信号又可分为光学、电化学、磁学、相态、形状等。刺激响应型材料在光动力治疗、信息存储、光催化、仿生材料、防伪及光电器件等领域具有广阔的应用前景而备受关注。本文致力于设计并构筑具有高灵敏度和选择性的多通道响应体系，在分子骨架中近配位点处组装生色团、氧化还原活性中心及荧光信号基团。这是一个新颖的研究领域，目前很少有多通道信号响应体系的文献报道，构效关系更不够明确。如何构筑具有高灵敏度、高选择性的实用响应体系，并研究其构效关系，对发展新型多通道响应智能材料具有理论指导意义。

二茂铁具有稳定性、可逆氧化还原性、易修饰性及生物相容性等优点，使其在刺激响应型材料领域具有重要的应用价值。我们合理构建二茂铁衍生物，系统研究在不同诱导条件下，具备多信号响应的功能材料。通过调节环腔尺寸、荧光基团和配位原子，进而提高系统的选择性和灵敏度,预期得到包括分子形态、线性、非线性光学以及磁性等多种响应信号。

基于二茂铁基菲罗啉 L1 的钌配合物具有电致变色及电致荧光变化的信号输出，归因于电氧化生成二茂铁鎓，产生了变色效应同时有效抑制了 PET 过程，体系荧光显著增强。施加还原电压后，二茂铁鎓还原为二茂铁，颜色及荧光均恢复原态，此体系具备良好的可逆性。

将含有此配合物的离子液体在 ITO 导电玻璃上构建了电控多信号响应装置，可以通过电压的数值变化可逆控制玻璃的颜色及荧光，且响应速度快。此装置拓展了此类材料的应用范围，进一步提高了系统的稳定性。

关键词：二茂铁，电化学

ABSTRACT

As one kind of the intelligent materials, stimuli-responsive materials exhibit physical or chemical property changes in response to external stimuli. In this context, it is of special interest is to construct and characterize multichannel responsive systems, which can lead to the acquisition of multiple signal expressions with high sensitivity and selectivity. Toward this goal, the receptors can be built by combining chromogenic units, redox-active groups, or fluorescent signaling subunits near the binding sites. This is a new area because relatively few multi-channel signaling examples have been reported. Also the mechanisms that regulate the interaction between probes and their targets are often poorly understood. A better understanding of the relevant interaction mechanisms will be of significant help in a rational approach to such goals.

Ferrocene-based functional materials have attracted considerable interests in the fields of catalysts, anticancer drugs, molecular sensors and optoelectronic materials. In the construction of multichannel responsive platforms, ferrocene has been found to be one of the most favored building blocks due to the availability, stability, reversible redox activity and tailorability. Our group has embarked on the systematic study of multichannel responsive platforms based on ferrocene with the target to sense different kinds of stimulus. The selectivity and sensibility can be obtained through tuning cavity size, choosing suitable fluorophore, and incorporating mixed donor atoms. The linear and nonlinear optical, magnetic and bioactive properties are expected multichannel responses.

Here we demonstrate an electrofluorochromic and electrochromic compound, L1, a ruthenium-ferrocene system. With the application of oxidation voltage, the switch-on fluorescence accompanied with the color changes were obtained, due to the inhibition of PET of ferrocenium species. Then the reduction voltage could recover the system. To futher enhance the stability, extend and simplify the application, this electrochemical-stimuli-responsive complex has been used successfully in ITO devices with ionic liquid as solvent.

Keywords: ferrocene, electrochemistry

目录

摘要 I

ABSTRACT II

第一章 文献综述 2

1.1刺激响应型主体材料概述 2

1.2 二茂铁基响应材料的研究 8

第二章 实验 13

2.1前言 13

2.2 实验目的及意义 13

2.3 试剂与仪器 14

2.4 配体合成路线 15

2.4.1 2-二茂铁-1H-咪唑[1,10]菲罗啉 L1 的合成 16

2.4.2 (2-二茂铁-1H-咪唑[1,10]菲罗啉)-2,2’联吡啶钌配合物 L2 的合成 16

第三章 结果与讨论 17

3.1 配体及配合物表征 17

3.2 配体晶体结构表征 18

3.2.1 单晶培养 18

3.2.2 单晶测定及数据收集 18

3.3 电化学诱导多信号响应的研究 21

3.3.1 乙腈溶液中电化学诱导多信号响应的研究 21

3.3.2 基于 ITO 玻璃电化学控制多信号响应研究 24

第四章 结论与展望 26

4.1 结论 26

4.2展望 26

参考文献 26

致谢 26

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