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In this thesis, a hydrothermal technique, and build 10 new inorganic - organic hybrid compounds by elemental analysis, IR, TG, XRPD and single crystal X-ray diffraction were used to characterize the crystal structure, and thermal stability of these compounds sex, electrochemical behavior was studied, the main research results are as follows: 1. hydrothermal conditions, the choice of coordination ability of the transition metal Cu and Fe, were synthesized and characterized four kinds of d-metal modified polyoxometalate Compounds: [VW 12 O 40 ] [Cu (mbpy) 3 ] 2 · 4H 2 O (1) [VW 12 O 40 ] [Fe (mbpy) 3 ] 2 · 4H 2 O (2) [FeW 12 O 40 ] [Fe (mbpy) 3 ] 2 · 3H 2 O (3) Cu (VO 2 ) (mbpy) (PO 4 ) (4) ( mbpy = 5, 5'-Dimethyl-2, 2'-bipyridine) compounds 1 and 2 are isomorphic heterogeneous, the cationic metal center is replaced by a Cu Fe, the compound 3, Fe atoms in both the center of the cluster as Keggin-type atoms, and M-organic group as a cationic unit. Compound 4 is a byproduct of compound 1, showing the one-dimensional chain structure. 2 buckle cap or V atoms Cu atoms in favor of highly charged polyoxoanions remain stable, while also regulating the pH of Keggin clusters and surface properties of synthesized five kinds of buckle dual cap polyoxometalate compounds: [ Cu 2 (mbpy) 2 VW 12 O 40 ] [Cu 2 O (Ac) (mbpy) 2 ] 2 · 2H 2 O (5) {[Cu (mbpy)] 2 PMo 12 O 40 } [Cu (ombpy) (OH 2 ) 3 ] · H 2 O (6) [Co (mbpy) 2 ] 2 [PMo 7 Mo 5 O 40 (VO) 2 ] (7) [Fe (mbpy) 3 ] 2 [PMo < sub> 10 V 2 (VO) 2 O 40 ] · 2H) 2O (8) [Cu (mbpy) < sub> 2 ] [Cu (mbpy) (OH 2 )] [Cu 2 (mbpy) 2 (C 2 O 4 )] 2 [(VO 4 ) Mo 8 V 4 (VO) 2 O 36 ] (9) (ombpy = 5-methyl-2, 2'-bipyridine-5-carboxylic acid) compound 5 and 6 is a modified two-Cu cap Keggin type cluster structure. The difference is that the double-Cu compound 5 Keggin-type cap cluster structure in the ortho position, the compound 6 Cu cap on the Keggin-type dual cluster structure on the bit. Compound 7, 8 and 9 are double V cap Keggin type cluster structure, its dual hat in cell clusters on the bit position. 3 Keggin structure in the absence of more than three tungstate as building units, coordination through V have been assembled by a Sandwich-type sandwich six yuan {VO} ring structure: (H 2 tcy) 6 (Hbpp) 6 H-4 [VW 12 O 40 ] [(VO) 6 (SbW 9 O 33 )) 2]) 3.30 H) 2O (10) (bpp = 1, 3-D (4-pyridyll) propane, tcy = 1, 2, 4, 5-tetra (pyridin-4-yl) cyclohexanol) compound 10 in sandwich-type multi-cluster anions [(VO) 6 (SbW 9 O 33 ) 2 ] 6 - unit is made with a sandwich structure of two [B-α-SbW 9 O 33 ] 9 - building unit and a tetragonal pyramid by the {VO} construct composed of six-membered ring, in addition to the sandwich-type multi-cluster anions, but also exist Keggin type [VW 12 O 40 ] 4 - acid anion clusters. Coexist in a crystal structure of two nanoscale cluster anion compound is very rare.
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