溶剂控制的铜基金属-有机框架物的合成与荧光性能

Solvent-Dependent Synthesis and Fluorescent Properties of Cu (Ⅱ) Metal-Organic Frameworks

金属-有机框架物在荧光识别领域表现出良好的应用前景,为探究合成更为精确识别的物质,本文利用二羧酸配体(H_2PAIA=5-丙酰胺基间苯二甲酸)和硝酸铜通过溶剂调控合成了两例结构不同的铜基金属-有机框架物(MOFs){[Cu(PAIA)(H_2O)]·2H_2O}(1)和{[Cu_3(PAIA)_2(DMSO)(Pyridine)_(1.5)]}(DMSO:二甲基亚砜;Pyridine:吡啶)(2)。尽管由相同的金属离子和有机配体构筑而成,但显示出具有显著溶剂导向特征的不同框架结构:配合物1为三维NbO型拓扑结构,而配合物2为二维sql型拓扑结构。正是由于这些结构上的差异,导致两个配合物的荧光识别性能和疏水性能展现出显著的不同。配合物1能够同时识别Pb^(2+)和Ag^+离子,而配合物2只能识别Pb^(2+),对Ag^+没有明显的信号响应。配合物1的疏水角85.06°比配合物2的52.71°有显著的增加。

Metal-organic frameworks have promising potentials of for applications in the areas of fluorescence recognition. To explore more accurate identification of synthetic substancess, we synthesized two copper metal-organic frameworks（MOFs）, { [Cu（PAIA） （H2O） ]·2H2O} （1） and { [Cu3（PAIA）2（DMSO） （Pyridine）,.5] } （2） （ H2 PAIA = 5- （propionyl-A2-azanyl） isophthalic acid ; DMSO = dimethyl sulphoxide）, by the solvothermal reaction in the presence of H2PAIA under different solvents（ H2O and DMSO/H2O）. Synthetic investigations and structural analyses reveal that both MOFs show distinct frameworks with remarkable solvent-directed feature, although they are assembled from the same starting materials, i. e. , Cu（ NO3 ）2·3H2O with H2PAIA for complexes 1 and 2. The topological structures and fluorescent properties of the two coordination compounds show a significant difference. Complex I is a three-dimensional NbO-type topology, while the complex 2 is a two-dimensional sql-type topology. Complex 1 exhibits fluorescent recognition to both Pb2＋ and Ag＋ ions, while complex 2 exhibits fluorescent recognition of Pb2＋ ion. The water contact angle for complex 1 is 85.06°, while the water contact angle for complex 2 is 52. 71°.