| Polyoxometalate represent a vast class of inorganic materials with excellent physical andchemical properties, such as high negative charge, redox properties, adjustable pH andnano-sized structures, which attracted considerable promise for potential applications inmagnetic, catalysis and medicine. The design and synthesis new functional crystalline solidmaterial based on polyoxometalates using specific POM building blocks have become one ofthe main directions in POM chemistry. In this paper, we have obtained a series crystallinesolid material by using {MnV13} system, chiral Dawson-type and Anderson-typepolyoxometalates based on the point of molecular design, self-assembly, self recognition andsurface modification. The syntheses, structures and properties of these compounds wereinvestigated. With a conventional synthesis procedure, twenty-one POMs have beensynthesized, and characterized by element analysis, IR, UV-Vis and single-crystal X-rayanalysis. And the thermal stabilities, circular dichroism, adsorption, catalytic property,magnetic and electrochemical properties of the compounds have been partially investigated.1. Three3D purely inorganic porous crystalline material have been synthesized based on[MnV13O38]7-polyoxometalates and rare earth ion Ln3+(La3+and Ce3+), which possess thefeature of the stability in inorganic porous material and the versatility in MOFs. The POMinorganic porous material was employed as heterogeneous catalyst for the oxidation ofthiophenic sulfur. The result indicated that compound2is an simple preparation, easy recycle,reusable and high activity catalyst. Meanwhile, the adsorption properties of the crystallineporous material was investigated.H[La(H2O)4]2[MnV13O38]·9NMP·17H2O (1)H[Ce(H2O)4]2[MnV13O38]·9NMP·17H2O (2)H[La(H2O)4]2[MnV13O38]·8NMP·9H2O (3)2. Three trimeric polyoxovanadate based on [MnV13O38]7-polyoxoanion withlanthanide cations Ln3+(Ln=La, Ce and Nd) and nicotinic acid have been synthesized.Compound4-6representing the first example of polyoxovanadate-based trimericaggregate with rare earth ions. The electrochemical and electrocatalytic properties of thecompounds have been investigated. Magnetic studies indicate that antiferromagneticinteractions exist in the compound5. This study provides a model reaction for preparingnano-sized crystalline solid materials based on POM, which have a potential functionalcharacteristics in electronic, optical and magnetic fields.H[{KLa2MnV13O38}3(SO4)2]·3(C6H6NO2)·57H2O (4) H[{KCe2MnV13O38}3(SO4)2]·3(C6H6NO2)·47H2O (5)H[{KNd2MnV13O38}3(SO4)2]·3(C6H6NO2)·45H2O (6)3. A series of {MnV13}-based inorganic-organic hybird compounds have beenconstructed by using [MnV13O38]7-, rare earth ions, DMF and isonicotinic acid underconventional aqueous solution method. The {MnV13} building blocks in compounds7-8are connected by rare earth-DMF complex to form a one-dimensional chain. Incompounds10-11,[MnV13O38]7-polyoxoanions were linked by {Ln2(C6H5NO2)3(H2O)6}to obtained a one-dimensional structure. The organic ligands play the role of theprotective and templating agents in the reaction. Furthermore, lanthanide contractionphenomenon of rare earth ions lead to a significant impact on the structure of thecompounds. The electrochemical and electrocatalytic properties of the compounds havebeen investigated. Magnetic studies indicate that antiferromagnetic interactions exist inthe compounds.H[{La2(DMF)5(H2O)4}{MnV13O38}]·DMF·5H2O (7)H[{Ce2(DMF)2(H2O)7}{MnV13O38}]·0.5DMF·5.5H2O (8)H2[{K(H2O)2}2{Nd(DMF)(H2O)3}{MnV13O38}]·5H2O (9)H[{La2(C6H5NO2)3(H2O)6}{[MnV13O38}]·C6H5NO2·10H2O (10)H[{Ce2(C6H5NO2)3(H2O)6}{MnV13O38}]·C6H5NO2·10H2O (11)H2.5[{Pr(C6H5NO2)(H2O)3.5}{Pr0.5(H2O)2}{MnV13O38}]·0.5C6H5NO2·10H2O (12)4. The chiral Dawson-type polyoxoanions [P2Mo18O62]6-racemic have beenseparated in aqueous solution with L,D-histidine, respectively. Two pairs ofenantiomerically compounds have been synthesized. We have also study the effects ofdifferent amino acids proportion for chiral transfers. Provides the premise applications ofthe chiral Dawson-type [P2Mo18O62]6-in the field of asymmetric catalysis, chiralseparation and biomedical.H3(L-HC6H9N3O2)3[P2Mo18O62]·10H2O (13)H3(D-HC6H9N3O2)3[P2Mo18O62]·10H2O (14)H4(L-HC6H9N3O2)2[P2Mo18O62]·21H2O (15)H4(D-HC6H9N3O2)2[P2Mo18O62]·21H2O (16)5. A series of high-dimensional hybird POM crystalline solid material have beensynthesized by Anderson-type [Al(OH)6O18]3-as building blocks and aminoacid-transition metal or rare earth coordination complexes as functional unit. Compounds18-21are built up of polyoxoanions [Al(OH)6O18]3-linked by rare-earth cations to form aone-dimensional chain, then adjacent chains are further connected by hydrogen bonds ofproline and free water molecules to3D supramolecular structure. The photocatalystproperty of compound18indicating an excellent photocatalyst of RhB dye underUV-irradiation. [(Gly)2Cu]K3[Al(OH)6Mo6O18]·9H2O (17)(C5H9NO2)2[La(H2O)7AlMo6H6O24]·11H2O (18)(C5H9NO2)2[Ce(H2O)7AlMo6H6O24]·11H2O (19)(C5H9NO2)2[Pr(H2O)7AlMo6H6O24]·10H2O (20)(C5H9NO2)2[Gd(H2O)7AlMo6H6O24]·10H2O (21)... |
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