Solvothermal Syntheses And Assembly Of Ge-O, Ti-O Clusters

Interest in Ge-O and Ti-O clusters is rapidly increasing because of their intriguingarchitectures and excellent properties. Clusters denoted as Ge7Ge8Ge9Ge10are themain building-blocks for constructing Ge-O clusters. These compounds exhibit a varietyof structures with a tendency of oxygen-sharing. The counterions of these Ge-OClusters are usually the protonated organic amines and metal amine complexes. Butlittle is known about related Ge-O clusters integrated with trnsition metal complexes aslinkages into the structures of germanates. The ethanolamine is an excellent chelatingagent and its metal complexes show peculiar spectroscopic property and will be a newtemplating reagent.Ti-O clusters as a precursor of titanium oxygen material haveattracted considerable interest, because they are new type of materials with properties ofcatalysis,photodegradation reaction. This work is devoted to studying the solvothermalmethod to prepare novel Ge-O and Ti-O clusters, and characterizing their structures andoptical properties. The major studies of this work are as follows:In introduction, the research progresses in metal oxygen clusters are reviewedbriefly; crystal structures and properties of the Ge-O clusters are summarized indetail;Then structure and recent development of Ti-O clusters are described specifically.In chapter2, under solvothermal condition, ethanolamine was used as structuraldirecting reagent for synthesis of Ge-O clusters and compounds [Ni（H₂O）（μ-C₂H₆-NO）₂Ge₇O₁₄（C₂H₇NO）]·C₂H₅OH （1） were obtained,structure and spectral properties ofthe compounds1are discussed briefly. The ethanolamine is a unique solvothermalsolvent for preparing germanates, because it has both aliphatic amine group andgermanium affinitive hydroxyl group.In chapter3, four compounds Ti₆O₄（o-BDC）₂（o-BDC-iPr）₂（OiPr）₁₀（2）, Ti₆O₃（o-BDC）₂（OiPr）₁₄（3）,（OOCCH₂COO）₂Ti₆O₁₇（CH₃CHCH₃）₁₄（4）, and （OOCC₂H₄COO）₂ Ti₆O₁₇（CH₃CHCH₃）₁₄（5） were obtained by solvothermal reactions. Structure analysisshows that theTi-O sub-clusters can combined into large cluster through thedicarboxylic acid ligand. The photochromic behavior of Ti-O clusters and itsphotocatalytic degradation of methyl orange are studied.