【作者】 陈晓彤；

【导师】 童爱军；

【作者基本信息】 清华大学 ， 化学， 2011， 博士

【摘要】 本文以水杨醛与氨基化合物生成水杨醛腙席夫碱类衍生物的反应为基础，合成了一系列分子结构简单、制备成本低廉的新型聚集荧光增强型分子。这类化合物的特点是：水杨醛席夫碱结构中的羟基与亚胺基形成了“六元环”分子内氢键结构，共轭体系之间通过氮-氮单键或碳-氮单键连接，在溶液中沿单键方向发生的分子内自由旋转会使分子激发态能量发生非辐射衰变而无荧光，而在固态（聚集态、晶态或薄膜态）时分子内旋转受到分子堆积效应的阻碍而荧光增强。本文以具有以上骨架结构的系列分子为基础，通过其结构与荧光性质的相关规律，构建了基于水杨醛腙类分子聚集荧光增强现象的荧光探针体系及有机光学材料。在荧光探针体系的研究中，以分散于溶液中不发射荧光的分子为探针，通过探针与目标分析物结合形成聚集体而产生的聚集荧光增强信号，分别实现了对水溶液中污染物肼以及鱼精蛋白的荧光增强型分析检测，在体积比为30/4/66的乙醇/乙酸/水混合溶剂中对肼的检测限为80nM，在pH=9.16的缓冲水溶液中对鱼精蛋白的检测限为43ng/mL；制备了表面为水杨醛腙共价修饰的具有聚集荧光增强性质的介孔材料薄膜，基于水杨醛席夫碱结构对铜离子的络合作用，实现了固态薄膜探针对水溶液中铜离子的荧光淬灭型分析检测，在pH=5.13的缓冲水溶液中对铜离子的检测限为0.8μM，该薄膜探针至少可以循环使用45次。上述三种探针均具有响应时间短、选择性好、灵敏度高的特点，并可用于实际样品的分析检测。在有机光学材料的研究中，本文制备了两类固态荧光性质可控的光学材料，一类以苯胺水杨醛腙分子结构为母体，通过改变分子结构中取代基的种类或位置来实现对所得晶体颜色/形貌的调控；另外一类以二水杨醛缩肼分子结构为母体，引入了有助于使固态分子形成亚稳态堆积模式的基团，通过加热或压力的外界刺激使固态分子在亚稳态与稳态之间转换而产生不同的固体荧光，得到了具有热致/压致固体荧光变色性质的光学材料。上述两种材料均具有合成路线与晶体制备方法简单的优点，对于分子结构与发光性质之间关系的研究具有重要意义，并有望在OLED及其它功能光学材料的研究中获得应用。更多还原

【Abstract】 In this dissertation, a series of salicylaldehyde hydrazone (SH) derivativeswere synthesized by condensing salicylaldehyde and amine compounds withease-preparation and low-cost. Intramolecular H-bonds of salicylaldiminemoieties allowed the nonradiative intramolecular rotation of two planarπ-conjugated moieties only around N-N or C-N single bond when moleculeswere dissolved in solvents. Therefore, potential aggregation-induced emissionenhancement (AIEE) properties of SH derivatives could be promised by therestriction of free intramolecular rotation in aggregate/solid state.Structure-property relationships of SH derivatives were utilized to constructfluorescence detecting systems and organic optical materials on basis of AIEE effect. Inthe respect of fluorescence detecting system, facile methods for the determination ofhydrazine and protamine have been developed based on fluorescence turn-on effect ofaggregate production; the limit of detection (LOD) of hydrazine in EtOH/HAc/H2O(30/4/66) was80nM, and that for protamine in buffer solution (pH=9.16) was43ng/mL. Also, an SH immobilized hybrid mesoporous materials with AIEE propertieswas prepared, and further utilized as a solid fluorescent sensor for reproducibledetection of Cu(II) ions based on fluorescence-off signal, with an LOD of0.8μM inbuffer solution (pH=5.3). The above three methods are with short response time, highselectivity and sensitivity, and could be used for detecting practical samples. On theother hand, two kinds of organic optical material with AIEE properties were prepared:firstly, a series of salicylaldimine crystals with color/morphology tunable propertieswere obtained by changing substituents; secondly, a crystalline solid of salicylaldehydeazine derivative with switchable solid-state fluorescence in responsible to externalthermal and piezochromic stimulus was obtained, which resulted from two distinctivecrystalline lattices via different π-π interactions. The facile synthesis andcrystal-preparing procedures favors the further theoretic exploration and practical use.更多还原