| In the history of coordination chemistry,the synthesis and study of metal clusters have always been one of the most popular research topics for researchers.And metal cluster compound with cubane structure but also with its unique electronic structure,different from the domain of electron cloud and plenty of space structure has been widely research,and applied to the bionic simulation chemistry,catalysis and molecular magnetism,and other fields,for example with cubane structure manganese metal clusters[Mn4O4]can simulate the plants photosystem II(PSII)oxygen-evolving complex(OEC)in the active site.In addition,a single type of metal clusters has been unable to meet people's requirements in some fields,so attention has been paid to the synthesis and research of two or more metal clusters.Heteronuclear metal clusters have different active centers which can co-catalyze the reaction and enhance the excellent properties of the materials.Among the factors affecting the synthesis of metal clusters,the selection of ligand is very important for the cluster.Tri-substituted methanol ligands are easy to form metal clusters with cubic structure.In general,each tri-substituted methanol ligand can bind three metal coordination centers,and the alcohol hydroxyl oxygen in the middle serves as the bridge atom connecting the three metal centers.In conclusion,it is of great practical significance to synthesize heteronuclear metal clusters with cubic structure.The first chapter of this paper is the introduction.It simply introduces the concept,classification and application of metal clusters,and introduces the synthesis methods and influencing factors of metal clusters.It focuses on the influence of metal ions and ligands on the synthesis of metal clusters.The applications of homonuclear and heteronuclear metal clusters with cubic structure in biomimetic simulation,catalytic reactions and monomolecular magnets are emphasized.In the second chapter,two new ligands,2-(hydroxy(bipyridin-2-yl)methyl phenol(H2L1)and 2-(Hydroxy(bi-phenol-2-yl)methyl)phenol(H4L2),were successfully synthesized from tri-substituted methanol.Three kinds of heteronuclear metal clusters with cubic and cubic alkane-like structures were prepared by different coordination experiments.[Fe2IIICo2II(L1)4]·(Cl O4)2(1),[Fe2IIINi2II(L1)4]·(Cl O4)2(2),[Fe4IIINa2I(HL2)4(Hpiv)2(piv)2]·Et3N(3),and their crystal structure,elemental analysis and magnetic properties were characterized.In the third chapter,the synthesis methods of two other tri-substituted methanol ligands,namely 1,1-Di-pyridin-2-yl-propane-1,3-diol(H2L3)and 2,6-Bi-(Hydroxy(pyridin-phenol-2-yl)methyl)phenol(H4L4),were introduced.Six transition metal clusters with different structures were prepared together with the ligand H2L1:[MnIII(H2L2)2(Me CN)2]·(Et3NH)·(Me OH)(4),[Mn2III(HL2)2]·(Et3N)·(Me CN)(5),[Cu4II(HL3)2(OAc)6](6),[Fe2III(H2L4)2(NO3)2]·(NO3)2(7),[Fe3III(HL4)(H2L4)Cl4]·(Me OH)5(8),[Mn3IIMn2III(L4)2(OAc)4(Me OH)2]·(CH2Cl2)(9).The fourth chapter summarizes the above chapters. |
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