Construction And Properties Of Metal Complexes Based On Tetrazole Derivatives

In recent years, coordination polymers have attracted widely attention,owing to a wide variety of potential applications, such as luminescence, magnetic, gas storage and separation. The tetrazole derivatives with multiple sites and flexible modes, they bond metal ions to form polymer with novel structures. The azide ion and carboxylic acid ion are able to effectively propagate magnetic exchange as bridging ligands, and have rich bridging modes, and transmit diversity of magnetic coupling.The tetrazole of coordination polymers with azide and tetrazole, carboxylic and tetrazole, they not only make structures of polymers more novel, but also have unique properties of magnetic.In this thesis, a series of complexes with one, two and three dimensional structures were synthesized by transition metal ions and Ln(III) lions, tetrazole derivates and / or azide ions. The 13 complexes were characterized by single crystal X-ray analysis,spectrum analysis, IR, elemental analyses, and some of them have also been characterized by magnetic measurements. The main points are as follows:1. Coordination compounds with 4-(pyridinyl)tetrazole(4-pytz)The 4-(pyridinyl)tetrazole(4-pytz), which contains both pyridyl and tetrazolate, has been explored widely in coordination chemistry, but has seldom reported in magnetochemistry. So we investigated the coordination chemistry and magnetism of4-pytz.We have synthesized one compound(1) with 3D by the situ hydrothermal reaction of 4-ptz and transitional metal ion of Co(II). In compound 1, metal ions are linked by the mixed azide and tetrazolate to four nuclear units. The units form a S one dimensional chain by tetrazole bridge. Magnetic studies demonstrated that compound1 consists of a ferromagnetic-like layer and exhibits spin glass dynamic relaxation.2. Coordination compounds with 5-phenyl-1H-tetrazole(5-HPT)We have synthesized one compound 2 by the reaction of 5-HPT, azide andtransitional metal ion of Co(II). Azide and tetrazolate form a Co4O2(ON)2 cubane unit.A Co12 cluster based on three identical Co4O2(ON)2 cubane units bridged by aμ6-carbonnate ligand is linked by π … π stacking interactions between phenylene groups, forming a 3D supramolecular structure. Magnetic investigations indicate that compound 2 exhibits long-rang ferromagnetic ordering.3. Coordination compounds with 5-(1H-tetrazol-5-yl)isophthalic(H3TZI)The 5-(1H-tetrazol-5-yl)isophthalic(H3TZI), which contains both tetrazole and carboxyl group, has been studied widely in coordination chemistry, but has seldom reported in magnetochemistry. The ligand has various coordination modes, and be able to transmit magnetic coupling. Based on above consideration, we studied the coordination chemistry and magnetism of H3 TZI.We have synthesized five compounds(3-7) by the reactions of H3 TZI and transitional metal ions of Cu(II), Co(II), Ni(II), Cd(II). In isomorphous compounds([M2(TZI)(OH)(H2O)]), metal ions are linked by the(μ-tetrazolate)(μ3-OH).Theμ3-OH bridged three metal ions to give one dimensional strip-shaped chain, and then by the H3 TZI to give three dimensional structural. The net topology with the point symbol(43)(4462)(4768). Magnetic analyses indicate that compound 3 shows the coexistence of spin canting, metamagnetism and antiferromagnetic ordering. Whereas compounds 4 and 5 exhibit spin canted antiferromagnetic coupling. Compound 7 is mononuclear unit, considering weakly coordination, the carboxylate and Zn(II) is bidentate state, by the H3 TZI to give three dimensional structure. Compound 6 and 7show blue shift, may be attributed to the π…π* intraligand charge transfer transitions.We synthesized three compounds(8-10) by the reactions of H3 TZI and Mn(II) ion.Compound 8 shows 3D structure based on tetrazolate and carboxylic. The neighboring Mn(II) and Na(I) are connected by(μ-N1,N2-tetrazolate)(μ-Ocarboxylate),and through hydrogen bonds and H3 TZI to give 3D structure. Compound 9 exhibits a1 D double chain. The neighboring Mn(II) ions are linked by the TZI to give a 1D double chain. The double chains are associated into a 2D hydrogen-bonded layer by interchain hydrogen bonds. The 2D layers through the TZI ligands into a 3D structure.In compound 10, metal ions are linked by the mixed(μ3-OH)(μ-N1, N2-tetrazolate)(μ-carboxylate) triple bridges and(μ3-OH)(μ-carboxylate) double bridges. The units are bridged by TZI to give a 1D chain, the chains through TZI to give a 3D structure.We try our best to obtain pure phase, but in vain. Magnetic analysis shows an antiferromagnetic interaction. The magnetic about compound 10 is testing.We have synthesized three compounds(11-13) by the reactions of H3 TZI and metal ions of Dy(III), Tb(III) and Gd(III). Single crystal X-ray analysis showed that compounds 11, 12 and 13 are isomorphous. The caxboxylic groups and metal ions are bidentate and double coordination. The metal ions are linked by TZI to give a 1D chain. The compounds 11, 12 and 13 have a number of water in their structures,through hydrogen bonds to give a 3D structure. Compounds 11, 12 and 13 of the magnetic data are testeing.