Synthesis And Characterizations Of Sulfonates And Aluminogermanates With Novel Open Frameworks

Recent years, coordination polymers have received great attention due to their widespread applications in catalysis, separation, adsorption, nonlinear optical, magnetic chemical, ion exchange and other fields. Great efforts have been made to synthesis novel sulfonates and germanates because of not only the coordinated flexibility of their structures but also the potential applications in their respective fields.In this thesis, two sulfonates have been synthesized by natural evaporation method and two new aluminum fluorides and three germinates have been synthesized under sovlothermal conditions. All of the crystal structures were determined by single crystal X-ray diffraction and their properties have been structurally characterized by infrared spectroscopy (FT-IR), thermogravimetric (TG), power X-ray diffraction (XRD), scanning electron microscopy (SEM). The main results are as follows:1. Two 0-D discrete metal sulfonates, [Ni(en)(H₂O)₄](1,5-nds).2H₂O (1) and [Ni(en)₂(H₂O)₂](1,5-nds).2H₂O (2), have been synthesized by natural evaporation method, in which 1,5-naphthalenedisulfonic acid acts as raw material. They belong to monoclinic system and space group is C2/c. Sulfonic acid anions, nickel coordination cations and water molecules interact through hydrogen bonds to form a three-dimensional supramolecular framework. However, the coordination environments of the two compounds are different. In compound (1), nickel is coordinated by four water molecules and one ethylenediamine ligand, while in compound (2), nickel is coordinated by two water molecules and two ethylenediamine ligands.2. Two aluminum fluorides, Al₂F₁₀[N₄C₆H₂₂] (3) and (H₃O)AlF4 (4), with different dimensions have been synthesized by using different organic templates under sovlothermal conditions. Compound (3) belongs to monoclinic system and space group is P 2(1)/ n, in which triethylenetetramine acts as organic template. It is a 0-D discrete structure, which is composed by Al₂F₁₀ dimers and triethylenetetramine. And they interact through hydrogen bonds to form a supramolecular framework. 2-D layered compound (4) belongs to tetragonal system and space group is I4/mcm, in which triethylamine acts as organic template. It is composed by the octahedral AlF6. The protonated water molecules involved strong hydrogen bonds with the fluorine atoms in the layers.3. Three new germanates, InGe₃O_7.5(C₂N₂H₈) (5), [C₂NH₈][AlGe₃O₈] (6) and [(AlGe₃O₈)_1.5 (en)_0.5] [Ni(en)₃] (7), with three-dimensional open framework have been synthesized under sovlothermal conditions. Compound (5) belongs to triclinic system and space group is P-1. It consists of layers constructed by four-membered rings, six-membered rings and eight-membered rings, in which Ge atoms act as skeleton elements, and then In₂O₆N₄ dimers connected the layers to form a 3-D indium-germanate. Compound (6) belongs to tetragonal system and space group is P4(3)2(1)2. The TO4 tetrahedron acts as based unit and connects with each other by sharing common oxygen atoms to form a three-dimensional GIS topology aluminogermanates. Compound (7) belongs to cubic system and space group is Pa-3. It is built by TO4 tetrahedrons, which acts as based unit. At last, we get an aluminogermanate with ten-membered rings in the final framework.