叔丁基螺二胺类化合物的合成及荧光探针与小分子催化性能的研究

发布时间：2018-08-13 13:47

【摘要】：聚集诱导荧光是一种特殊的发光现象,即分子在溶解状态时荧光很弱,而在聚集态时则表现出强荧光。与传统荧光染料相比,聚集诱导荧光分子可以有效避免由聚集所引起的荧光淬灭作用。经由水杨醛和氨基之间的简单缩合反应得到的西弗碱衍生物,正是一类拥有此种独特发光性质的分子。在西弗碱结构中,西弗碱与邻位羟基通过分子内氢键形成了稳定的六元环,该结构使整个分子自由旋转受阻,由此带来了聚集诱导荧光的发光特征。结合螺双芴的三维正交结构及摩尔吸光系数大、荧光量子产率高等性质,本论文在螺双芴的结构基础上,引入水杨醛西弗碱结构以构筑一类新的聚集诱导发光体系,将在开发新型荧光探针及固体发光材料领域有较大的前景。此外,探索了手性螺二胺化合物的小分子催化性能。本文工作分为以下两个部分:第一部分:合成了两种具有聚集诱导发光性质的西弗碱类荧光探针SPF-T1和SPF-T2。首先,以含螺双芴结构的西弗碱SPF-T1为探针,研究其对金属离子的识别。实验结果表明,探针对铜离子、钴离子和锌离子有识别作用。其中铜离子和钴离子对探针的吸收光谱有很大影响,溶液颜色由无色变为黄色,检测极限分别为为0.15μM和0.12μM。对锌离子表现出聚集诱导荧光增强现象,检测极限为0.3μM。而且SPF-T1作为锌离子探针用于细胞成像。其次,将三芳胺单元引入SPF-T1结构中,得到了具有发黄色固体荧光的材料SPF-T2,同样能用作荧光增强型锌离子探针,检测极限为0.063μM。通过紫外检测钴离子和铜离子,检测极限分别为0.084μM和0.073μM。SPF-T2的聚集诱导性能更加明显且具有双光子吸收性能。第二分:将轴手性的螺二胺应用于小分子不对称催化反应,用于开发新型手性催化剂。成功的催化了Michael加成反应及Friedel Crafts反应。得到了较好的收率,分别为75%和86%,但在不对称催化方面没有较好的表现。
[Abstract]:Agglomeration induced fluorescence is a special luminescence phenomenon, that is, the fluorescence of molecules is very weak in the dissolved state and strong fluorescence in the aggregation state. Compared with traditional fluorescent dyes, agglomeration induced fluorescence molecules can effectively avoid fluorescence quenching caused by aggregation. Sieverine derivatives obtained by simple condensation reaction between salicylaldehyde and amino are a class of molecules with this unique luminescent property. In the sieverbase structure, sieverine and o-hydroxyl group form a stable six-member ring through intramolecular hydrogen bonding, which hinders the free rotation of the whole molecule, resulting in the luminescence of aggregation induced fluorescence. Combined with the three dimensional orthogonal structure of spirobifluorene and its high molar absorptivity and high fluorescence quantum yield, a new aggregation induced luminescence system was constructed by introducing the structure of salicylaldehyde-sieverine on the basis of the structure of spirobifluorene. It will have a great prospect in the field of developing new fluorescent probes and solid state luminescent materials. In addition, the catalytic properties of chiral spirodiamine compounds were investigated. The work of this paper is divided into two parts as follows: in the first part, two kinds of fluorescence probes SPF-T1 and SPF-T2 with aggregation induced luminescence have been synthesized. Firstly, the recognition of metal ions was studied by using sieverine SPF-T1 with spirobifluorene structure as a probe. The results show that the probe can recognize copper, cobalt and zinc ions. Copper ion and cobalt ion have great influence on the absorption spectrum of the probe. The color of the solution changes from colorless to yellow. The detection limits are 0.15 渭 M and 0.12 渭 M, respectively. The concentration induced fluorescence enhancement of zinc ion was observed, and the detection limit was 0.3 渭 M. And SPF-T1 is used as a zinc ion probe for cell imaging. Secondly, the triarylamine unit was introduced into the SPF-T1 structure to obtain a yellow solid fluorescence material SPF-T2, which can also be used as a fluorescence enhanced zinc ion probe with a detection limit of 0.063 渭 M. By UV detection of cobalt ion and copper ion, the aggregation inductive performance of the detection limit of 0.084 渭 M and 0.073 渭 M.SPF-T2 is more obvious and the two-photon absorption property is more obvious. Second, the axial chiral spirodiamine was applied to the asymmetric catalytic reaction of small molecules to develop new chiral catalysts. Michael addition reaction and Friedel Crafts reaction were successfully catalyzed. The yield was 75% and 86%, respectively, but there was no good performance in asymmetric catalysis.
【学位授予单位】：上海师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.3

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