The Synthesis And Structure Of Novel Bis(Triol)-Functional Anderson Cluster Derivatives

The organic-inorganic hybrids based on polyoxometalates(POMs)have drawn tremendous attention.Especially,the Anderson-type POMs possess of naturally attractive planar structures,which have much potential to construct organic-inorganic hybrid chains due to the six protons attached to ?3-O atoms can be replaced conveniently.So the Anderson-type POMs should be one of the best candidates for forming organic-inorganic hybrid chains which possess of naturally attractive planar structures with two groups of active sites on both sides and the organic ligands can be grafted either or opposite one another to form steady bi-substituted;And to connect Anderson clusters into chains,the active bridging bis(Triol)-ligands containing two claws are geometrically well-suited which have also aroused much concern.However,the design and synthesis of Anderson POMs covalently incorporated into organic-inorganic hybrid chains is a significant challenge,a multistep control strategy is the key factor.Herein,five novel bis(Triol)-functionalized Anderson cluster derivatives(POM-L-POM,POM-L,L-POM-L)were efficiently synthesized which are typical example of a multistep control strategy.To our knowledge,compound 1a and compound 1b are the first confirmatory structure of dumbbell-type Anderson clusters,as well as compound 2-3 are the first derivatives containing free Triol "claw".Compound 1-4 still remain ?3-OH or free claws reactive sites on the both sides which could serve as potential synthons to form organic-inorganic hybrid chains with the multistep control strategy presented in this paper.Interestingly the compound 1 is endowed the molecular recognition function and the free claws of compound 3 construct H-bond network which initially manifest the astonishing self-assembly properties.Furthermore the cluster 1 also presents synergistic effect in electromagnetic properties.Compound 1-3 have been fully characterized by single-crystal X-ray diffraction,FT-IR,ESI-MS,]H NMR spectroscopy,and thermal gravimetric analyses(TGA).