Design, Synthesis And Application Of Terpyridine Ruthenium Complex Metal Organic Framework (MOF

Coordination polymers（CPs）,also known as metal organic frameworks（MOFs）,have been emerging as a popular class of porous crystalline materials in the past decades.A unique advantage of MOFs is that their topological structures can be designed at the molecular level.And both building units of MOFs,organic linkers and inorganic nodes,can be modified within a great synthetic scope.At the macro level,the chemical and physical properties of MOFs are determined by their geometric morphology as well as the intrinsic characteristics of their building units.Incorporation of light sensitive or redox active units in the MOFs structures can not only render the functions of these building units to the MOFs material,but also generate new functions due to potential synergistic effects between building units within the specific spatial environment of MOFs.In this thesis work,novel MOFs were prepared using bis tripyridyl ruthenium complexes as linkers and their photocatalytic applications were explored.The main content of this thesis includes following sections:（1）A series of eight carboxylate modified bistripyridine ruthenium complexes were synthesized,including biscarboxylic acid[Ru^Ⅱ（tpy COO^–）₂]（PF₆）₂ and[Ru^Ⅱ（tpy–ph COO^–）（tpy COO^–）]（PF₆）₂complexes;tricarboxylicacid[Ru^Ⅱ（tpy–ph COO^–）（tpy（COO^–）₂）]（PF₆）₂,[Ru^Ⅱ（tpy COO^–）（tpy（COO^–）₂）]（PF₆）₂,and[Ru^Ⅱ（tpy–ph（COO^–）₂）（tpy COO^–）]（PF₆）₂complexes,and tetracarboxylic acid[Ru^Ⅱ（tpy–ph（COO^–）₂）（tpy（COO^–）₂）]（PF₆）₂,[Ru^Ⅱ（tpy（COO^-）₂）₂]（PF₆）₂,and[Ru^Ⅱ（tpy–ph（COO^–）₂）₂]（PF₆）₂ complexes.（2）Two novel metal organic frameworks（MOFs）were designed and synthesized using dicarboxylate ruthenium complex[Ru^Ⅱ（tpy COO^–）₂]（PF₆）₂ as a linker and zirconium or hafnium cation as a node.Their photocatalytic performance were studied for oxidation reactions and degradation of organic dyes.And it has been proven that the metal organic framework has the ability to degrade the organic dye peacock green under photocatalysis.Zr–（COOH）₂ and Hf–（COOH）₂ can degrade 78.6%and 71.0%of malachite green,respectively.In addition,the conversion rates of Zr–（COOH）₂ and Hf–（COOH）₂ photocatalytic oxidation of benzylamine were 99%and 43.7%,respectively.（3）Three-dimensional metal organic frameworks were prepared using tricarboxylic acid[Ru^Ⅱ（tpy–ph COO^–）（tpy COO^–）]（PF₆）₂ or tetracarboxylic acid[Ru^Ⅱ（tpy（COO^-）₂）₂]（PF₆）₂ as a linker and copper cation as a node.a Photocatalytic degradation of dyes by these MOFs was studied.Cu–（COOH）₃ and Cu–（COOH）₄ as catalysts can degrade 90.64%and 87.57%malachite green,as well as 90.64%and 87.57%methylene blue,respectively,under xenon lamp irradiation.