Syntheses,Structures And Functions Of Organoic Derivatives Of Anderson-evans Polyoxometalates

Polyoxometalates are a class of metal oxide cluster consisting of pre-transition metal ions and oxygen ligand.There are numerous varieties and complicated structures of POMs.Owing to their rich properties of photo,electron,magnetism,catalysis and bioactivity,there are many potential applications in the field of catalysis,material and medicine.Organic covalent functionalization of POMs is the derivatives formed by the terminal oxide,bridged oxide or addenda metal atoms replaced by organic ligand.Organic functionalization of POMs is the current hotpot and because it can improve the function of POMs.Up to now,two strategies,namely,pre-functionalization and post-functionalization,had been developed to modify POMs.In this thesis,we had devoted to the preparation,structure and function of organic derivatives of Anderson-Evans POMs.There are in the following three parts in this thesis:Firstly,through the strategy of post-functionalization,two molecular rods containingthebackboneofAndersonPOMs,namely,[Bu₄N]₃[Mn Mo₆O₁₈（（OCH₂）₃CN=CH-4-Py）₂]（POM-1）and[Bu₄N]₃[Mn Mo₆O₁₈（（OCH₂）₃CN=CH-3-Py）₂]（POM-2）were prepared through the imidization reaction betweentheprecursorof[Bu₄N]₃[Mo₆O₁₈{（OCH₂）₃NH₂}₂]and3-pyridinecarboxaldehyde/4-pyridinecarboxaldehyde.Using POM-1 and POM-2 as linking ligand and[Cu（Ph₃）₂（CH₃CN）₂]Cl O₄（Cu P2）as node,a coordination polymer of（TBA）n{[Cu（PPh₃）₂]₂（POM-1）·4DMF}n（1）with 1D chain-like structure,two coordination polymer of（TBA）n{[Cu（PPh₃）₂]₂（POM-2）}n（2）and{[Cu（PPh₃）₂]₃（POM-1）}n（3）with the structure of 2D network were obtained.Those coordination polymers maintain the skeleton until 230^oC and omit green luminescence upon the excitation of UV-light,which can be used as potent green-light materials.Secondly,through the strategy of post-functionalization,a series of organic derivatives of Anderson POMs were obtained through the imidization reaction between the precursor of[Bu₄N]₃[Mo₆O₁₈{（OCH₂）₃NH₂}₂]and 1-naphthaldehyde,2-naphthaldehyde,4-quinolinecarboxaldehyde,9-anthraldehyde,1-pyrenecarboxaldehyde,3-bromobenzal-dehyde,4-bromobenzaldehyde,4-iodobenzaldehyde,ferrocenecarboxaldehyde,respectively.Those organic derivatives of Anderson POMs can be connected into 1D infinite chain and 2D network via C-H···O hydrogen bonding,π···πinteractions and halo-oxygen interactions.Compared to corresponding ligands,those compounds have more intense luminescent intensity and shorter luminescent wavelength,they are also a class of potent POMs-based luminescent materials.Thirdly,through the strategy of post-functionalization,a series of TRIS-R ligands were synthesized by the amidation reaction of tris（hydroxymethyl）aminomethane with carboxylic acid containing Iodide atom.Tris（hydroxymethyl）aminomethane and 2-iodobenzoyl chloride,3-Iodobenzoyl chloride,4-Iodobenzoyl chloride,3-Iodo-4-aminobenzoyl chloride,3,4-diiodobenzoyl chloride and 2,3,5-triodobenzoyl chloride are amidated respectively,which are reacted with octamolybdates and Mn（CH₃CO₂）₃ to afford a series of Iodo-containing organic derivatives of Anderson POMs.Compared to the precursor of Anderson POMs,most compounds demonstrate increased inhibitory activity on the virus of EV71 and CVB3and the tumor cells of Hela and Hep-2.