负载染料分子的酰胺基功能化PMOFs荧光传感材料的构筑与性能研究

Porous metal-organic frameworks (PMOFs) have become a research hotspot in the field of coordination chemistry because their structures can be tailored and functionalized. The studies on fluorescent sensing the common volatile organic compounds (VOCs) in indoor and outdoor environment by using PMOFs are of great theoretical and scientific significance. However, the researches on the fluorescent sensing VOCs materials constructed from the PMOFs loaded by organic fluorescent dyes are very limited. In this project, three types of amide-based ligands were designed and synthesized, and various organic carboxylates were selected as the auxiliary ligands to assemble with transition metals under the solvothermal conditions, aiming for constructing the amide-based functionalized PMOFs. By utilize the supramolecular recognition functions of amide groups in the pores of PMOFs to capture organic fluorescent dyes, obtaining new fluorescent materials derived from the amide-based PMOFs loaded by dyes. We will investigate the fluorescent influence of VOCs on PMOFs loaded by dyes to realize the aim of fluorescence sensing. The effect of organic solvents on the structures of pores and frameworks of the PMOFs will be investigated by adjusting the sizes and categories of organic solvents. The influence of structural characteristics of the organic ligands on the frameworks and pores of the PMOFs will be studied. The assemble regulars will be summarized to realize the controllable synthesis of PMOFs. The intrinsic relation between the structures and properties will be explored. This project for broadening the practical application of PMOFs materials in the fields of molecular recognition and fluorescent sensing has important scientific significance.

多孔金属-有机骨架（PMOFs）由于结构可剪裁和易功能化的特点已成为配位化学领域的研究热点。PMOFs作为荧光材料对室内外环境中常见的挥发性有机化合物(VOCs)的传感研究具有重大的理论和科学意义，然而利用PMOFs负载有机荧光染料制备VOCs荧光传感材料的研究十分有限。本项目旨在设计合成三类酰胺基配体，并以有机羧酸为辅助配体，在溶剂热条件下与过渡金属配位组装构筑酰胺基功能化PMOFs；利用PMOFs孔道中酰胺基的超分子识别作用捕获荧光染料分子，获得负载染料分子的PMOFs材料；通过测定VOCs对负载荧光染料分子的PMOFs发光性能的影响来实现传感作用。通过调控溶剂分子的尺寸、种类以及配体的结构特性等来研究其对PMOFs孔道和骨架结构的影响，总结组装规律，实现PMOFs的可控合成；探索结构与性能之间的关系。本项目的实施对拓展PMOFs材料在分子识别、荧光传感等领域的应用有重要的科学意义。

本项目中设计合成14种酰胺基有机配体[3-(吡啶-3-氨基甲酰)吡嗪羧酸(3-HPPA)、3-(2-吡啶羧酸)氨基吡啶(3-HPCAP)、(3-吡啶基)异烟酰胺(3-PIA)、N,N'-双(3-吡啶甲酰胺基)-1,3-丙烷(3-BPYP)、N,N'-双(3-吡啶基)丙二酰胺(3-BPMA)、N,N'-双(3-吡啶)己二酰胺(3-BPAA)、N,N'-双(3-吡啶基)-辛二酰胺(3-BPOA)、N,N'-双(3-吡啶基)癸二酰胺(3-BPSA)、N,N'-双(3-吡啶基)环己烷-1,4-二酰胺(3-BPCD)、4,4'-(乙烯-1,2-二取代基)双(3-吡啶基)二酰胺(3-EBPBA)、1,4-双(3-吡啶基)萘二酰胺(3-BPNA)、1,4-双(4-吡啶基)萘二酰胺(4-BPNA)、2,6-双(3-吡啶基)萘二酰胺(3-BPNDA)和2,6-双(4-吡啶基)萘二酰胺(4-BPNDA)]分别与14种有机芳香羧酸[1,2-苯二甲酸(1,2-H2BDC)、1,3-苯二甲酸(1,3-H2BDC)、1,4-苯二甲酸(1,4-H2BDC)、1,2-苯二乙酸(1,2-H2PDA)、1,4-苯二乙酸(1,4-H2PDA)、1,4-萘二酸(1,4-H2NDC)、5-硝基间苯二甲酸(5-H2NIP)、3,5-二硝基苯甲酸(HDNBA)、2,5-噻吩二羧酸(2,5-H2TDC)、4,4'-联苯醚二羧酸(H2OBA)、1,3,5-苯三甲酸(1,3,5-H3BTC)、1,2,4,5-苯四甲酸(H4BTEC)、1,3,5-三(4-苯甲酸)苯(H3BTB)和5-(4'-羧基苯氧基)间苯二甲酸(H3CPPA)]在水热/溶剂热条件下反应制备得到了34个金属有机配合物(配合物1–34)，并通过元素分析、红外光谱、热重分析、单晶X射线衍射以及粉末X射线衍射等进行了结构表征。有机芳香羧酸和酰胺基有机配体的刚性、长度、非配位取代基以及金属离子的半径对配合物的结构的影响被系统研究。此外，部分配合物的光催化、吸附、固体荧光以及荧光传感行为也被研究。通过调控溶剂分子的尺寸、种类以及配体的结构特性等来研究其对配合物孔道和骨架结构的影响，总结组装规律，实现多孔金属有机骨架(PMOFs)的可控合成；探索结构与性能之间的关系。本项目的研究为新的催化、吸附及荧光材料的合成提供了重要的实验和理论依据。