| Polyoxometalates (POMs) chemistry including iso-POMs and hetero-POMs is an important branch of inorganic chemistry. Polyoxometalates anions are good molecular receptors because of their properties such as strong storage ability of electron and proton, and can be assembled to the supramolecular compounds by combining with inorganic elements, organic molecules (including macrocyclic compounds) and/or ions. It can develop many new properties and obtain the specific functional molecular material. Specially, organoimido derivatives of POMs are a kind of new organic-inorganic hybrids. On the one hand, those species are remarkable for their important optical, electronic, magnetic, catalytic and medical properties owing to their strong interaction involving d-πorbits and p-πelectrons. On the other hand, organoimido derivatives of POMs being a new unit can construct many complicate hybrids, and the preparation of these hybrids are also easily controlled. Therefore, it becomes a front topic of POMs chemistry.In this dissertation, organoimido derivatives of POMs based on Lindqvist with a phenolic hydroxyl have been modified on the basis of previous studies using DCC dehydration method, and a series of organoimido derivatives of POMs with extra organic functional groups have been achieved to use esterification reaction for further chemical modification.Mono-functionalized organoimido derivative of POMs, (n-Bu4N)2 [Mo6O18(NAr)] (Ar = o-CH3C6H3-p-OH)(1) and bifunctionalized organoimido derivative of POMs, (n-Bu4N)2 [Mo6O17(NAr)2] (Ar = p-C6H4OH)(2) have been synthesized with 4-amino,2-methyl phenol and 4-amino phenol as the organic ligands respectively. Elemental analyses, IR, UV-Vis, 1HNMR spectra and X-ray single crystal diffraction have been carried out for the new compounds. (n-Bu4N)2 [Mo6O18(NAr)] (Ar = o-CH3C6H3-p-OH) belongs to Monoclinic, C2/c space group, and (n-Bu4N)2 [Mo6O17(NAr)2] (Ar = p-C6H4OH) belongs to Orthorhombic, Pbcn space group. In their crystal lattices, several O - H…O hydrogen bonds between a cluster anion and its two neighbors arrange the cluster anions of 1 into zigzag chains and arrange the cluster anions of 2 into a lamellated structure, and the organoimido ligands are sandwiched by hexamolybdate clusters.On the basis of [Bu4N]2-1((n-Bu4N)2 [Mo6O18(NAr)] (Ar = o-CH3C6H3-p-OH)), severalnew organic -inorganic hybrids have been synthesized by DCC-assisted esterification with carboxylic acids, with anhydride of acetic acid and with chloride of acid, and we obtainedthe crystal structure of the derivatives of [Bu4N]2-1 with acetic acid, 4-chlorobenzoic acid,propanoic acid, propenoic acid and anhydride of acetic, respectively. Elemental analyses, IR, UV-Vis, 1HNMR spectra and X-ray single crystal diffraction have been carried out for thenew compounds. All these derivatives belong to Triclinic, P(?) space group. All the results show that the hybrid [Bu4N]2-1 have realized esterification reactions with carboxylic acidsand the targeted hybrids have formed indeed. The research greatly enrich chemistry of organoimido derivatives of POMs.The interaction between bifunctionalized organoimido derivative of POMs, (n-Bu4N)2 [Mo6O18(NAr)2] (Ar = o-CH3C6H3-p-OH ) and BSA has been studied by SPR, and the results show that there are the static electricity among them.In summary, this dissertation can expand preparation of derivatives of POMs, and it can lead us to explore and develop new materials through further understanding and finding the relationship between structure and specific performance of such organic-inorganichybrid materials .
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