多酸阴离子作为构筑块自组装合成新型功能化合物

This research project aims at the design and synthesis of polyoxometalates(POMs)-based inorganic-organic hybrid materials. Using POMs as building block unit, we synthesized POMs derivatives of benzamide and p-phenylenediamine by the linking of coordination bond, and characterized these products by elemental analysis, IR, UV, XPS, X-ray powder diffraction, 1H NMR and 183W NMR measurement. We explored the rational method to prepare these inorganic-organic hybrid materials. Some them appeared to be the nano-sized particles and had high oxidative catalytic activity. In addition, we synthesized Mo(V)-oxo-cluster inorganic-organic hybrid materials having tunnel structures and determined their crystal structures. The role of ethyldiamine as both template and reductant has been proved for the first time. There exist a network of multiple-point hydrogen bonds in their crystal structure. These hybrid compounds have high oxidative catalytic activities for the reaction of the oxidation of acetaldehyde into acetic acid with H2O2, showing that the hybrid compounds may become promising oxidative catalysts. By the layer-by-layer electrostatic self-assembly technique, we successfully prepared various POMs based nanocomposite film materials having the photoluminescent or the third-order nonlinear optical (NLO) properties. The structure and surface pattern of these films were investigated by UV-Vis, small-angle XR, XPS, AFM and the photoluminescent or the third-order nonlinear optical properties of these functional films were also studies. This is first example to prove the possibility of the preparation of POMs -based photoluminescent films. We also found that the combination of POMs anion with phthalocyanine bi-CoPc in the films can modify the third-order NLO properties of bi-CoPc. The result is of considerable significance to explore the POMs-Pc type of third-order nonlinear optical materials.

多酸阴离子作为无机构筑块和有机组分靠分子识别自组装形成具有微孔、导电性、磁性的新型功能化合物。本课题用杂多蓝作为无机组分与适当选择的有机分子结合成为有序的分子聚集体固态结构，通过单晶结构测定和固体核磁等表征方法研究其结构和性能的关系，是一项多酸化学与材料科学交叉领域的具有重大学术意义和应用前景的前尚课题之一。