Synthesis Of Keggin Type POM-based Cu-olefin Complexes

The synthesis of POM-based compounds with novel structural types has always been a core hotspot in the field of POM chemistry.As one of the six basic structures,Keggin-type POM is the most explored structure type so far,and the derivatives prepared based on this structure have been of great concern.This paper focuses on the synthesis of olefin-containing POM-based compounds,by designing an olefin-containing dimethylthiotetrazole ligand(Lx)and introducing it into the Keggin-type POM hybrid system,and successfully obtaining six cases of Keggin type POM-based Cu-olefin compounds with different structures by hydrothermal synthesis.The analysis of X-ray single crystal structure shows that due to the design and introduction of the novel ligand Lx,the structure of the compound presents the bonding of classical(Cu-O/N bond)and non-classical(metal-olefin double bond),which greatly enriches the coordination mode of POMs compounds.In particular,the successful design and synthesis of this ligand not only adds the structural type of the POM-based compounds,but also additionally imparts the solubility of the compound in a variety of organic solvents such as acetonitrile and DMSO.Electrospray ionization mass spectrometry(ESI-MS)studies have shown that compound 1 can dissociate a variety of structural components in acetonitrile solvents,such as[PMo₁₂]^3-,[(PMo₁₂)Lx]^3-,[(Cu Lx)(PMo₁₂)]^2-plasma fragments.In addition,studies such as infrared and Raman have shown that compounds have high stability performance during dissolution.Using this solubility property of the compound in an organic solvent,we used a simple and efficient solvent diffusion method to prepare a spherical POM-based nanoparticle,which realized the transition of the compound from a bulk crystal to a nanosphere.The realization of this preparation process provides a completely new synthetic path for the preparation of nanomaterials.