Synthese, Structures, And Properties Study Of Novel Supramolecular Compounds Based On Polyoxometalates

In this thesis, three novel polyoxometalate (POM) supramolecular assemblies based on macrocations clusters, metal-organic compounds and polyoxometalates have been synthesized via supramolecular interaction and coordination bonds. Moreover, a new series of high dimensional metal—oxogen clustes supramolecular networks have also been synthesized by choosing various of 3d or 4f metal ions with different coordination capacities and organic ligands with different space configuration. The study on synthetic conditions and rules for these new compounds, the effect of various auxiliary ligands on the ultimate structures, topological analyses, the principle of molecular self-assembly, and the exploration of relationships between structures and properties for these new compounds are also carried out.Nine new polyoxometalate and high dimensional metal—oxogen clustes supramolecular compounds have been synthesized on the basis of hydrothermal technique and/or convenient aqueous solution synthesis methods and structurally characterized by elemental analyses, IR, UV/Vis spectrum, XRPD, TG and single crystal X-ray diffractions. The thermal stabilities, magnetic properties and fluorescent activity of these compounds have been studied.1. Three new supramolecular compounds based on polyoxometalates and metal-organic cations building blocks have been synthesized and structurally characterized. We have also discussed the influence of various important factors to the cluster packing style. Among these compounds, compound 1 is the first ionic crystal supramolecular assembly base on unusual triple-Dawson-type polyoxoanions [P₂W₁₆MnIII₂O₆₀]₃^24- and bipyramid-like 3d-4f heterometallic clusters [CeIV₃MnIV₂O₆(OAc)₆(H₂O)₉]²⁺. Compound 2 represents a new and rare supramolecular example constructed by MnIII-salen Schiff-base building blocks andβ-octamolybdate isopolyoxoanions, which combines POMs chemistry and Schiff-base chemistry two interesting fields together to prepare new hybrid materials. Compound 3 represents the first example of a pure inorganic 3D (8,3)-connected structural topology based on the [H₂W₁₂O₄₂]^10- building blocks and CuII linkers. Na₂₀[CeIV₃MnIV₂O₆(OAc)₆(H₂O)₉]₂[P₂W₁₆MnIII₂O₆₀]₃·21H₂O (1) [N(CH₃)₄]₂[Mn(Salen)(DMF)₂]₂[β-Mo₈O₂₆]·2DMF (2) KNa₃[Cu(H₂O)₂{Cu(H₂O)₃}₂(H₂W₁₂O₄₂)]·16H₂O (3)2. Six new 3d or 3d-4f high dimensional metal—oxogen clustes supramolecular networks have been successfully synthesized by rational selecting and in situ ligands synthesize new organic ligands and different 3d or 4f metal ions on the basis of hydrothermal technique. We further study the effect of various of metal ions with different coordination capacities, the length and flexility of organic ligands, and mixed ligands on the ultimate structures of these compounds. Compounds 4-5 are modulated synthesize by introduction of various auxiliary ligands into an in situ ligands synthesis system of terephthalonitrile. Compound 4 contains a new type of 1D zigzag ladders, which are further interlocked with the other two identical ones, forming a 3D polycatenated framework. Compound 5 displays a new 3D''inclined''interpenetration architecture based on 2D undulated layers. Compounds 6-9 are four new anion-templated 3D heterobimetallic host-guest supramolecular assemblies based on the lanthanide-carboxylate layers and copper(I)-inic pillars. [Ni₂(TP)₂(BPP)₂(H₂O)₂]_n (4) {[Co(TP)(BPP)]₄·6H₂O}_n (5) [Ln2(1,2-bdc)₂(H₂O)₂Cu(inic)₂](ClO₄) (Ln = Eu (6), Tb (7), Nd (8) , Sm (9))...