Study On Several Metal Clusters Based On Tert-butylphosphonate As Ligand

Tert-butylphosphonate ligand has excellent coordination properties.Metal clusters which modified by it have many kinds of structures and get more attention in the field of material applications.Especially in the field of single-molecule magnets?SMM?,catalysis and so on.In this thesis,we used tert-butylphosphonic acid as a ligand to study the interaction between the various metals with it.Seven different kinds of metal clusters were obtained by using the analytical pure metal salts as the starting materials without further purification,or preparing Ln?hfac?₃?Ln=Y,Pr,Gd,Dy?as precursors.The complexes were mainly characterized by means of single crystal XRD,elemental analysis and magnetic test.The main contents can be divided into the following three parts according to the type of metal ions contained in the complexes.?1?The synthesis and characterization of a bismuth cluster with tert-butylphosphonate ligand.It was obtained by using Bi₉O₇?hfac?₁₃,^tBuPO₃H₂ as raw materials reacted in the mixed solution of CH₂Cl₂ with CH₃OH.?2?The synthesis and characterization of a manganese cluster and a cobalt cluster with tert-butylphosphonate ligand.The manganese cluster was obtained by reacted?CH₃COO?₃Mn with ^tBuPO₃H₂ in the mixed solution of CH₃CN with CH₃OH.The cobalt cluster was obtained by reacted?CH₃COO?₂Co with ^tBuPO₃H₂ in the mixed solution of CH₃CN with CH₃OH.?3?The synthesis and characterization of a yttrium cluster,a praseodymium cluster,a gadolinium cluster and a dysprosium cluster with tert-butylphosphonate ligand.Ln?hfac?₃?Ln=Y,Pr,Gd,Dy?,^tBuPO₃H₂ were used as starting materials and which were reacted in methanol solution.It is demonstrated that experimental conditions,such asthe ratio of tert-butylphosphonic acid with bismuth,the solvent system and other factors have a great impact on the formation of bismuth cluster;tert-butylphosphonate has stronger coordination capacity with manganese compared with carboxylate ligands and crown ether ligands during the room temperature;the interaction of tert-butylphosphonate with cobalt is very strong and the amount of tert-butylphosphonic acid must be controlled strictly or will get precipitation during the experiment;the coordination properties of tert-butylphosphonate with some rare earth metals have lots of similarities and it's easy to get the same structure of the metal clusters.