| The aim of this thesis is the synthesis of new polyoxometalate compounds on the basis of saturated and non-saturated Keggin-type polyoxotungstates and Anderson-type polyoxoanion clusters, which are bridged by transition metal compounds. The study on synthetic conditions and rules for these new compounds are also carried out. Eight new polyoxometalate compounds and one coordination compound have been synthesized under conventional and hydrothermal conditions and structurally characterized by elemental analyses, IR, TG and single crystal X-ray diffractions.1. Two new polyoxometalate compounds on the basis of non-saturated Keggin-type polyoxoanion cluster have been synthesized and structurally characterized: [Co(en)2]4[Co4(Hen)2Si2W18O68]·H2en·6H2O (1) NaH3[CoⅢ(en)2(OH)SiW11CoⅡO39]·9.25H2O (2)Compound 1 is constructed from trivacant Keggin polyanions linked through tetrameric cobalt unit, which coordinates with organonitrogen ligands. Moreover, the sandwich-type polyoxoanions were linked by Co2+ ions into a straight chain. Compound 2 exhibits an interesting 1D chainlike architecture which consists supporting monosubstituted Keggin polyoxoanion and a novel dinuclear Co metal-unit. 2. Five new polyoxometalate compounds on the basis of saturated Keggin-type polyoxoanion cluster have been hydrothermally synthesized and structurally characterized: [Cu(phen)2]4[α-SiW12O40] (3) {Cu3(4,4'-bpy)2(2,2'-bpy)3}{Cu(2,2'-bpy)2}{α-SiW12O40}·0.5(H2O)·0.5(4,4'-bpy) (4) [Cu4(4,4'-bpy)3(2,2'-bpy)4][α-SiW12O40]·H2O (5) [Cu(4,4'-bpy)(4,4'-Hbpy)0.5]2[PW12O40] (6) [Cu3Cl(4,4'-bpy)3]2[α-SiW12O40]·4H2O (7) Compound 3 exhibits interesting chiral layer constructed from interperpendicular helical chains. Furthermore, the chiral layers are connected by the [α-SiW12O40]4– anions via hydrogen bonding interactions to form a 3D superamolecular structure. Compounds 4 and 5 are packed together via the aromaticπ-πstacking interactions and exhibit an interesting 3D sandglasslike"host"network with 1D channels, in which [α-SiW12O40]4– anions"guests"reside. Compound 6 is composed of cationic Cu(I) coordination polymer chains and discrete [PW12O40]3– polyoxoanions, generating a 3D interpenetrating superamolecular structure. Compound 7 has a unique 2D superamolecular network, which is composed of cationic trinuclear Cu(I) coordination polymer chains and discrete [α-SiW12O40]4– polyoxoanions as linkers.3. On the basis of transition metal and amino acid, two new compounds have been synthesized and structurally characterized: Na3[Cu(gly)2][Cr(OH)6Mo6O18]·13H2O (8) NaCo2(gly)6ClO4 (9)Compound 8 exhibits the first example of a 3D extended framework based on Anderson type polyanions and amino acid molecules. Compound 9 consists of an unusual 3D network grafted with Na[Co(gly)3]6 complexes. Moreover, compound 9 contains left-handed and right-handed helical chains.
|
PDF Full Text Request