【作者】 张晓霞；

【导师】 李亚平； 刘遂军；

【作者基本信息】 山西大学 ， 有机化学， 2023， 硕士

【摘要】 配位聚合物是一种新型有机-无机杂化材料,具有可控的结构、明确的发光位置,所以更适用于传感和检测应用。配位聚合物的构筑受多种因素影响,如配体、金属离子、溶剂和温度等。合理选择有机配体,采用合适的方法合成配位聚合物,并探究其发光性能具有现实意义。本文以发光性能良好的富氮V型半刚性3,5-双（1-苯并咪唑基）吡啶（BBIP）为主配体,结合不同辅助羧酸配体,在酸-碱混合配体策略下成功合成了七种过渡金属配位聚合物。通过结构表征和性能测试,我们发现,部分配位聚合物具有较高的化学稳定性,以及优良的发光性能,重点对其荧光传感性质进行了探究,主要内容如下:1.以三种二元芳香羧酸为辅助配体,与Cd^Ⅱ/Zn^Ⅱ在水（溶剂）热条件下成功构筑了四种配位聚合物1-4。结构分析表明,配位聚合物1-4具有不同的结构维度（1为三维结构,2和3为二维结构,4（JXUST-30）为一维双链结构）,这与酸碱配体的连接方式有关。配体的配位点越多,配位方式越复杂,越易形成高维结构。荧光传感实验表明,Al³⁺和Cr³⁺对1具有荧光猝灭效应,检出限分别为0.061μM和0.070μM;4（JXUST-30）可作为多响应传感器,以荧光增强效应识别乙酰丙酮、乙二醛和水杨醛,且响应时间较快、灵敏度较高、循环性能优良。另外,我们制备了基于4（JXUST-30）的荧光器件（便携式荧光试纸、复合薄膜和LED灯珠）,为检测有机小分子的实际应用提供了可能。2.以共轭性较强的2,6-萘二酸为辅助配体,在水（溶剂）热条件下,通过调控溶剂的比例和金属离子（Cd^Ⅱ/Zn^Ⅱ/Co^Ⅱ）,成功制备了三种配位聚合物5-7。单晶结构解析表明,5-7都表现出二重互穿4-连接的sql拓扑结构,但由于中心金属配位数的不同,5-7中2,6-萘二酸存在螯合和单齿两种配位模式。荧光传感实验表明,配位聚合物7可作为一种多响应传感器,以荧光增强效应识别乙酰丙酮和H₂PO₄^-,以荧光猝灭效应识别水杨醛,且都表现出高选择、高灵敏性,检出限分别为0.103 m M、0.121μM和0.606μM。上述发光配位聚合物对目标分析物表现出快速的荧光响应,证明其可作为一种刺激响应材料为分子识别和传感应用提供潜在的平台。更多还原

【Abstract】 Coordination polymers are a new type of organic-inorganic hybrid materials with controllable structure and clear luminous position,which can be used in sensing and detection applications.The construction of coordination polymers is affected by many factors,such as ligands,metal ions,solvents,temperature and so on.It is of practical significance to reasonably select organic ligands,adopt appropriate methods to synthesize coordination polymers and explore the luminescent properties.Seven coordination polymers have been synthesized under the design of acid-base mixed ligands by using nitrogen-rich v-shaped semi-rigid 3,5-bis（1H-benzo[d]imidazol-1-yl）pyridine（BBIP）with good luminescent properties as the primary ligand and different auxiliary carboxylic acid ligands.Through structural characterization and performance testing,we found that some coordination polymers have high chemical stability and excellent luminescence properties,so the fluorescence sensing properties are studied.The main research contents are as follows:1.Four coordination polymers 1-4 were successfully prepared with Cd^Ⅱ/Zn^Ⅱby solvothermal method using three aromatic dicarboxylic acids as auxiliary ligands.Structural analysis shows that coordination polymers 1-4 have different structural dimensions（1 has a three-dimensional structure,2 and 3 have a two-dimensional structure,and 4（JXUST-30）has an one-dimensional double-chain structure）,which is related to the connection mode of acid-base ligands.When the ligand has more coordination sites and more complex coordination modes,it is easier to form high-dimensional structure.The fluorescence sensing experiments show that 1 has fluorescence quenching effect on Al³⁺/Cr³⁺,and the detection limits are 0.061μM and 0.070μM,respectively.4（JXUST-30）could be used as a multifunctional fluorescence turn-on sensor for detecting acetylacetone,glyoxal and salicylaldehyde with fast response time,high sensitivity and excellent cycle performance.In addition,we prepared portable fluorescent test strips,composite films and LED lamp beads based on 4（JXUST-30）,which provided the possibility for the practical application of fluorescence detection of small organic molecules.2.Three coordination polymers 5-7 were successfully prepared by adjusting the ratio of solvents and metal ions（Cd^Ⅱ/Zn^Ⅱ/Co^Ⅱ）under the hydrothermal condition with strong conjugated 2,6-naphthalenedioic acid as auxiliary ligand.The analysis of single crystal structure shows that 5-7 are 4-connected sql topologies with double interpenetrated structures,but due to the difference of the coordination number of central metals,there are two coordination modes of 2,6-naphthalenedioic acid in 5-7:chelating and monodentate coordination.Fluorescence sensing experiments show that 7 could be used as a multi-response fluorescence sensor to recognize acetylacetone and H₂PO₄^-by fluorescence enhancement effect and salicylaldehyde by fluorescence quenching effect,with detection limits of 0.103 m M,0.121μM and 0.606μM,respectively.更多还原