新型含羟基二芳烯光化学金属离子传感器的构建及性质研究

发布时间：2019-01-05 15:59

【摘要】：由于具有出色的光致变色性质、热稳定性和抗疲劳性,二芳烯最初在高密度信息存储方面的潜在应用引起了人们广泛关注。近年来,基于二芳烯的多重调控荧光开关和光化学传感引起了人们的广泛关注,这些新的功能将进一步推动二芳烯化合物的发展,对二芳烯的未来格局及应用带来全新的改变。目前,将二芳烯化合物作为光化学传感器已经成为一个新的研究热点,因此,设计合成新的对金属离子有独特响应的二芳烯正受到了广泛的关注。本论文通过分子设计、合成,将金属离子识别基团引入到含羟基的二芳烯分子中,构建了具有多重调控以及离子识别性能的二芳烯衍生物。着重研究了这些二芳烯的多重调控性能和对金属离子的光化学传感性能,包括多重调控的荧光开关、金属离子的荧光和比色传感器以及分子逻辑电路的构建等。具体研究内容和研究成果如下:第1章综述了光化学传感器的研究进展。结合二芳烯化合物的研究现状,综述了基于二芳烯的离子传感器的研究进展,提出研究课题。第2章设计合成了一种末端含水杨醛基团的二芳烯化合物。系统研究了其在光和酸/碱作用下的多重相应的光致变色性质。研究结果显示,该化合物具有优异的光致变色性质。去质子化后,闭环态的最大吸收波长红移了100 nm,荧光调制效率从30%提高到55%。第3章设计合成了一种不对称的含双-2-甲基吡啶胺的二芳烯化合物。系统地研究了其光致变色性质以及其与Zn~(2+)的相互作用。研究结果显示,该化合物在溶液和晶相中均表现出优异的光致变色性质。与Zn~(2+)的相互作用后,其荧光强度增强了2倍,并伴随着荧光的颜色从黑色变成了亮蓝色。证明了该化合物可以作为Zn~(2+)的荧光增强传感器。第4章利用Mannich反应,将双-2-甲基吡啶胺引入到末端含苯酚的二芳烯分子中。系统地研究了该化合物的光致变色性质以及与金属离子的相互作用。研究结果显示,其闭环态与Cu~(2+)作用后,其最大吸收波长从558 nm蓝移到504nm,吸收强度增加了3.3倍,并伴随着溶液的颜色从紫色到红色的显著变化。通过滴定实验数据分析,该化合物可以作为Cu~(2+)的比色传感器。第5章通过席夫碱单元,将二芳烯和8-氨基喹啉单元进行连接,合成了一个新的二芳烯化合物。系统地研究了该化合物在光和化学试剂作用下的多重调控性质。实验结果显示,该化合物对Mg~(2+)和Ca~(2+)具有较高的选择性和灵敏性,并表现出不同的荧光发射和颜色变化。证明了该化合物可以作为Mg~(2+)和Ca~(2+)的荧光/比色双通道传感器。此外,基于其多重调控性质,可以构建一个单分子的组合逻辑电路。第6章结论与展望
[Abstract]:Due to their excellent photochromic properties, thermal stability and fatigue resistance, the potential applications of diarylenes in high density information storage have attracted much attention. In recent years, the multilevel control fluorescence switch and photochemical sensing based on diarylene have attracted wide attention. These new functions will further promote the development of diarylene compounds and bring new changes to the future pattern and application of diarylerene. At present, diarylene compounds as photochemical sensors have become a new research hotspot. Therefore, the design and synthesis of new diarylerenes which have unique response to metal ions have been paid more and more attention. Through molecular design and synthesis, the metal ion recognition group was introduced into diarylerenes containing hydroxyl groups, and the diaryene derivatives with multiple regulation and ion recognition properties were constructed. The properties of these diarylenes in multiplex regulation and photochemical sensing of metal ions are mainly studied, including multiplex fluorescent switches, fluorescence and colorimetric sensors of metal ions, and the construction of molecular logic circuits, etc. The research contents and results are as follows: chapter 1 summarizes the research progress of photochemical sensors. In this paper, the research progress of diarylene-based ion sensors is reviewed, and the research topics are put forward. In chapter 2, a kind of diarylerene with water-terminated salicylidene group was designed and synthesized. The photochromic properties of the photochromic agents under the action of acid / alkali are systematically studied. The results show that the compound has excellent photochromic properties. After deprotonation, the maximum absorption wavelength of the closed-loop state is redshifted from 30% to 55%, and the fluorescence modulation efficiency of 100 nm, is increased. In chapter 3, an asymmetric diarylene compound containing bis-2-methylpyridine was designed and synthesized. The photochromism and its interaction with Zn~ (2) were studied systematically. The results show that the compound exhibits excellent photochromic properties in both solution and crystalline phase. After interaction with Zn~ (2), the fluorescence intensity increased by 2 times, and the color of fluorescence changed from black to bright blue. It is proved that the compound can be used as a fluorescence enhanced sensor for Zn~ (2). In chapter 4, Mannich reaction was used to introduce bis-2-methylpyridine into the diarylenes containing phenol at the end. The photochromic properties of the compound and its interaction with metal ions were systematically studied. The results show that the maximum absorption wavelength shifts from 558 nm blue to 504 nm after the interaction of the closed-loop state with Cu~ (2), and the absorption intensity increases by 3.3 times, and the color of the solution changes significantly from purple to red. The compound can be used as a colorimetric sensor for Cu~ (2) by analyzing the titration data. In chapter 5, a new diaryene compound was synthesized by connecting diarene with 8-aminoquinoline unit by Schiff base unit. The multiple regulation properties of the compound under the action of light and chemical reagents were systematically studied. The experimental results show that the compound has high selectivity and sensitivity to Mg~ (2) and Ca~ (2), and shows different fluorescence emission and color change. It is proved that the compound can be used as Mg~ (2) and Ca~ (2) fluorescence / colorimetric dual channel sensors. In addition, a single molecular combinatorial logic circuit can be constructed based on its multiple modulation properties. Chapter 6 conclusion and Prospect
【学位授予单位】：南昌大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：TP212.2

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