可调控孔径的d-f异金属有机框架作为硝基苯类爆炸物荧光探针研究

According to Hard-Soft acids and bases theory (HSAB theory), the nitrogencontaining organic polycarboxylic acids as the linkers with rational structures are designed and synthesized , as a result, carboxyl oxygen atoms of the ligands coordinate with the strong fluorescent rare earth ions and the nitrogen atoms of the ligands coordinate with the fluorescence transition metal ions， the d-f heterometal metal organic frameworks with micronanoporous structures can be achieved by self-assembling. Using porous heterometal metal organic frameworks structures , their unsaturated open coordination sites and highly sensitive characteristic fluorescence of rare earth ions on the coordination environment, they are investigated as the fluorescent probes of nitrobenzene explosive to ascertain the chemical mechanisms why MOFs with the different porous structures being the nitrobenzene explosive fluorescence probes. This investigation intends to realize the design ideas that ligands carry out the effective chemical regulation in the self-assembling process, so that some d-f heterometal organic frameworks fluorescent probes with novel structures are achieved. This study also elucidate the regulating law and influencing factors of the micronanoporous sizes and shapes, in which discover the coordination environment in nanometer holes with regard to the detected explosive and the chemical mechanisms that the rare earth ions sensitize or quench fluorescence. It can can provide the designing ideas, synthetic technology and basic theoretical guidance through this research in order to investigate d-f heterometal metal organic frameworks as the nitrobenzene explosive fluorescent probes.

根据软硬酸碱理论，设计并合成结构合理的含氮类有机多羧酸作为连接体，使配体的羧基氧原子与强荧光的稀土离子配位、氮原子与发光的过渡金属离子配位，通过自组装得到具有不同微纳米孔径结构的d-f异金属有机框架。利用其不同的孔径结构及金属离子的开放位点、稀土离子荧光对配位环境变化高度敏感的特性，研究其作为硝基苯类爆炸物荧光探针，探明不同的孔径结构作为硝基苯类爆炸物荧光探针的化学作用机理。本研究拟实现利用配体的尺寸在自组装过程中进行有效调控化学结构的设计思想，得到一些不同微纳米孔径的d-f异金属有机框架荧光探针，阐明其孔径大小和形状的合成调控规律，揭示被检测硝基苯类爆炸物对孔径中配位环境的影响因素以及对稀土离子荧光敏化或淬灭的化学机理。通过本研究，为设计和研制d-f异金属有机框架作为硝基苯类爆炸物荧光探针提供设计思想、合成制备技术和基础理论指导。

根据有关文献合成和购买了一些含吡啶基、含氮基官能团的有机多羧酸配体，如4,5-咪唑-二羧酸、2-(2'-吡啶)-苯并咪唑-5-羧酸、4-（2,2';6',2''- 三吡啶基）-4'-1,2-苯基二羧酸、3-(2,4-二羧基苯)-6-羧基吡啶、2,2'-联吡啶-5,5'-二羧酸、4-（2,2';6',2''-三吡啶基）-4'-1,2-苯基二羧酸、4-(2,2';6',2'')四吡啶-4'-苯甲酸、4-(吡啶-3-氧基)-邻苯二甲酸等有机多羧酸配体，选择发光的f区元素金属离子（Sm3+、Eu3+、Tb3+、Dy3+等）和一些d10结构过渡金属离子（Zn2+、Cd2+等）在水热/溶剂热条件下进行自组装反应，构筑了系列的d-f异金属、过渡金属、稀土金属有机框架。实验合成中主要采用水热/溶剂热反应条件，得到了系列的不同微纳米孔径结构d-f异金属有机框架、过渡金属有机框架、稀土金属有机框架。探究了d-f异金属、过渡金属、稀土金属有机框架作为硝基苯类爆炸物荧光探针的工作，阐明了不同孔径的金属有机框架结构作为硝基苯类爆炸物荧光探针的化学作用机理，为设计和研制d-f异金属有机框架作为硝基苯类爆炸物荧光探针提供设计思想、合成制备技术和基础理论指导作。.本研究实现了利用配体的尺寸在自组装过程中进行有效调控化学结构的设计思想，得到了一些不同微纳米孔径的d-f异金属有机框架荧光探针，阐明了其孔径大小和形状的合成调控规律，揭示了不同的硝基苯类爆炸物对稀土离子荧光敏化或淬灭的化学机理，阐明了金属有机框架和作为硝基苯类爆炸物荧光探针之间的关系及化学键作用。.本研究项目共发表了7篇论文，相关专利的申请正在进行中。