手性和非中心对称的多功能配位聚合物的合成及性质研究

Multifunctional coordination polymers as a new type of functional materials can simultaneously possess different properties, such as magnetism, fluorescence, nonlinear optics (NLO) and ferroelectricity properties, which are becoming a research hotspot in both domestic and overseas. The noncentrosymmetric and chiral coordination polymers usually have second-order nonlinear optics properties and they can even simultaneously possess both SHG and ferroelectricity properties when their space groups belong to the 10 polar point group, C1, Cs, C2, C2v, C4, C4v, C3, C3v, C6, C6v. Moreover, the target MOFs with both second- and third-order nonlinear optics properties at the same time can be obtained when the third-order NLO-active W(Mo)/S/Cu units are incorporated to the noncentrosymmetric or chiral MOFs. This strategy will give an enormous impetus to the advanced functional materials. In this project, we are going to synthesize noncentrosymmetric and chiral coordination polymers by utilizing a series of symmetric or asymmetric triangle ligands to assemble with transition metal ions or W(Mo)/S/Cu cluster units. We expect to obtain ferroelectric porous MOFs or even second- and third-order NLO-active MOFs. The utilization of a series of symmetric or asymmetric triangle ligands to construct noncentrosymmetric and chiral multifunctional MOFs may provide a new way to the synthesis of multifunctional crystalline materials.

多功能配位聚合物作为一种同时具有多种性质的新型功能材料，可以同时拥有磁性，荧光，非线性光学(NLO)，铁电等多种性质，越来越成为国内外各个课题组的研究重点。非中心对称及手性配位聚合物通常具有二阶非线性光学性质，当其所处的空间群为10种极性点群时，则会同时具有二阶非线性光学性质和铁电性质，此外，当我们在结构中引入具有三阶非线性活性的W(Mo)/S/Cu簇单元后，则有可能得到同时具有二阶、三阶非线性光学性质的MOFs，这对于先进功能材料的发展有着积极的推动作用。在本项目中，我们将利用一系列对称或不对称性的三角形配体和各种过渡金属离子或簇节点进行非中心对称和手性多功能配位聚合物的自组装，以期望得到具有铁电性质的多孔MOFs，甚至同时具有二阶、三阶非线性光学性质的MOFs。这种首次利用一系列对称和不对称三角配体用于构筑非中心对称和手性多功能MOFs的尝试，将为多功能晶态材料的合成提供一条新的途径.

多功能配位聚合物作为一种晶态材料在气体分离，重金属离子及含氧酸根离子的吸附分离，荧光识别等方面皆有着重要的应用。我们的研究内容主要集中在功能配位聚合物，W/S/Cu原子簇的合成及性质研究上。到目前为止，我们得到了53个配位聚合物以及3个原子簇聚合物的结构。经过梳理归纳，目前的工作重点集中在重金属离子及含氧酸根离子的吸附分离，MOF作为荧光识别器对爆炸物分子，重金属离子的吸附响应，原子簇聚合物的三阶非线性及催化性能等几个方面。