Synthesis And Characterization Of The Inorganic-organic Hybrid Metal Borates

With the rapid development of the study and application to inorganic-organic hybrid materials,inorganic-organic hybrid borates with complex structures and rich properties also become apopular area. In order to further enrich the structural chemistry of borates and synthesize novelinorganic-organic hybrid materials with specific optical, electrical and magnetic properties, theresearches on synthesizing new inorganic-organic hybrid borates are carried out. In this thesis,boric acid/borax, organic amines/organic acids, metal salts are used as materials. Five inorganic-organic hybrid metal borates have been synthesized under hydrothermal, solvothermal or solutionevaporation methods. Besides, in the process of synthesis lanthanum and copper borates, twocoordination polymers which do not contain B atom have been synthesized by hydrothermalmethod. The crystal structures have been determined from single-crystal X-ray diffraction data andfurther characterized by XRD, FT-IR spectrum and TG-DTA.（1） Amine containing inorganic-organic hybrid borates: four new inorganic-organic hybridborates with similar structure,[M（en）₃]₂（H₃BO₃）（WO₄）₂·6H₂O （M=Zn（1）, Co（2）） and[M（en）₃]₂（H₃BO₃）（MoO₄）₂·6H₂O （M=Zn（3）, Co（4）） have been synthesized in hydrothermallycondition. In these compounds, metal ion M2+coordinates to six N atoms from threeethylenediamine, forming a distorted octahedral [M（en）₃]₂+. W or Mo atoms coordinate to four Oatoms to form a tetrahedral （WO₄）₂-or （MoO₄）₂-. B atom exists in the form of boric acid. Theseisolated polyhedral cells, boric acid and free water molecules link through N―H…O andO―H…O hydrogen bonds, forming a3D supramolecular structure.（2） Organic acid containing inorganic-organic hybrid borate: a new inorganic-organichybrid borate Li₅B(C₈O₁₂H₄)·H₂O （5） has been synthesized by evaporation method. In compound5,boric acid and tartaric acid dehydrate form a [B（C₄O₆H₂）₂]^5-anion, then part of Li ions link withthis anion to form a three-dimensional structure with channels, while the other part of Li ions fill inthese channels to balance charge.（3） Coordination polymers of lanthanum and copper: two new compounds,[La₂（C₂O₄）_0.5（C₂H₃O₂）₅（H₂O）]·H₂O （6） and Cu₃O（OH）₃ClO₄（7）, have been synthesized inhydrothermally conditions. In compound （6）, La atoms coordinate with O from acetate, oxalato orwater molecules, forming a two-dimensional layer structure. Adjacent layers of the structure are linked by O―H…O hydrogen bonds and van der Waals, forming a3D supramolecular structure.In compound （7）, Cu atoms coordinate with hydroxyl oxygen, perchlorate oxygen or bridgingoxygen atoms to form CuO₆octahedra, the CuO₆octahedra link together through shared edge,forming one-dimensional chains. These one-dimensional chains are linked by ClO₄-forming3Dstructure. O―H…O hydrogen bonds are also widely present in the3D structure.