Fabrications And Functions Of Lindqvist Type Polyoxometalates Organic Derivatives

Due to its structural stability and easy preparation,Lindqvist-type polyoxometalates have received increasing attention from chemists in the recent years.And a series of organic-inorganic POM-based hybrids can be constructed by organic modification.Among them,organoimido derivatives of POMs have drawn people's attention.It is constructed by the covalent linkage between POMs and organic amine moieties,so the charge can be transferred through these two parts.However,current work is mainly focused on the synthetic chemistry and structural beauty of organoimido derivatives,and there are few studies on its application.Moreover,due to the fact that aromatic amine modified POMs are easy preparation and characterization,the majority of the current work is on the aromatic amine and few of them on aliphatic amine.To solve above problems,this work is trying to modify the Lindqvist-type POMs with functional moieties,including optoelectronic molecules and bioactive molecules,to design the functional POM-based materials and study their applications.The following are the main results of this paper:(1)The optoelectronic molecules oligoaniline have been introduced into the POMs system to obtain the POM-based organoimido derivatives.The conjugated interaction between POMs and organic moieties have endowed the hybrids with interesting redox properties,further acting as functional materials.To achieve that,we designed a series of oligoaniline functionalized POM derivatives,including di(aniline)monosubstituted hexamolybdates derivatives,di(aniline)disubstituted hexavanadates derivatives and tri(aniline)monosubstituted hexamolybdates derivatives.Furthermore,the stimuli responsive self-assembly behavior of tri(aniline)monosubstituted hexamolybdate derivatives has been investigated.(2)The bioactive molecule amantadine has been introduced into the POMs system as a model to study the synthesis,characterization and application of aliphatic modified organoimido derivatives of hexamolybdates.To achieve that,we designed and obtained the mono-,cis-di,trans-di and tri-substituted derivatives of hexamolybdates.Furthermore,the anticancer ability of mono-substituted derivatives on MCF-7 breast cancer cell has been investigated.(3)The degradable group has been introduced into the POMs system to design a degradable organoimido derivatives of hexamolybdates with high inhibitory performance towards glioblastoma cell.This design can endow the derivatives with high efficacy towards cancer cell and low toxicity towards normal cell.In addition,the magnetic behavior of lacunary Lindqvist-type hexamolybadates derivatives containing lanthanide metal has been investigated,which introduced a new modification approach for Lindqvist-type POMs.