【作者】 唐磊；

【导师】 吕萍；

【作者基本信息】 浙江大学 ， 有机化学， 2007， 硕士

【摘要】 本论文主要研究了9-亚环庚三烯基芴类荧光传感器的合成及对金属离子的响应。利用Sonagoshira偶联反应，合成了具有氮杂冠醚结构的9-亚环庚三烯基芴类的化合物，并通过氢谱、碳谱、质谱对合成的分子结构进行了表征。同时，我们利用紫外可见吸收和稳态荧光光谱仪，考察了这些化合物的光物理现象，发现化合物存在从离子传感部分到荧光发射部分的电荷转移（CT）。通过研究这些化合物对金属离子的响应，我们发现：在乙腈溶剂中，N,N-二乙二醇乙醚取代的9-亚环庚三烯基芴（7）对三价铁离子和二价铜离子有着灵敏的荧光响应以及很好的选择性(对Na⁺；Fe²⁺；Ag⁺；Zn²⁺；Co²⁺；Cd²⁺；Ni²⁺；Mg²⁺；Ca²⁺；Hg²⁺；Mn²⁺；K⁺；Ba²⁺；Li⁺；Pb²⁺；Cs⁺；Cr³⁺和Sm³⁺无响应)，表现为荧光淬灭；而通过N,N-二β-羟基乙基取代的9-亚环庚三烯基芴（8）和三价铁离子在甲醇中的荧光增强、8和二价铜离子在乙腈中的荧光增强现象，我们可以实现对三价铁离子和二价铜离子的识别。进一步研究表明，荧光增强是由于溶液中存在9-亚环庚三烯基芴和金属离子的纳米聚集体，由此产生聚集体荧光增强效应。我们分别通过透射电镜和动态光散射证明了纳米聚集体的存在，并就聚集体的形成机理进行了探讨。更多还原

【Abstract】 In this dissertation, 9-（cycloheptatrienylidene）fluorene derivatives function as fluorescent chemosensor for metal ions were designed and discussed.9-（Cycloheptatrienylidene）fluorene derivatives with heterocrown ether structure have been prepared by well known Sonagoshira coupling reaction, and their structures were characterized by ¹H NMR ¹³C NMR and MS. Their optical properties have been measured by UV-vis spectropHotometer and spectrofluorometer, which show the intramolecular charge transfer.2,7-Bis（2-（4-（di（2-（2-ethoxyethoxy）ethyl）amino）pHenyl）ethynyl）-9-（cyclohepta trienylidene）fluorine （7） exhibits high sensitivity and selectivity for Cu²⁺ or Fe³⁺ (no response to Na⁺; Fe²⁺; Ag⁺; Zn²⁺; Co²⁺; Cd²⁺; Ni²⁺; Mg²⁺; Ca²⁺; Hg²⁺; Mn²⁺; K⁺; Ba²⁺; Li⁺; Pb²⁺; Cs⁺; Cr³⁺ and Sm³⁺), and displayed quenched emission when either Cu²⁺ or Fe³⁺ was added into its acetonitrile solution. However, 2, 7-bis（2-（4-（di（2-hydroxyethyl）amino）pHenyl）ethynyl）-9-（cycloheptatrienylidene）flu orine （8） could successfully identify Fe³⁺ or Cu²⁺ by enhanced emission with addition of Fe³⁺ in its methanol or with addition of Cu²⁺ in its acetonitrile.With the futher study, we find that emission enhancement was ascribed to nano-aggregates formation, which was induced by supramolecular self-assembly between non-benzenoid hydrocarbons and metal ions through intermolecular electrostatic force in organic solvent. Both transmission electron microscope （TEM） and dynamic light scattering （DLS） proved the existence of nano aggregates.更多还原