Syntheses,Structures And Properties Of Cobalt/Nickel-Thiacalix[4]arene Complexes With Polyazole Ligands

Calixarenes are a kind of excellent multidentate ligands for the construction of cluster compounds because they have several phenolic hydroxyl groups and are easy to be modified.In this thesis,a series of cobalt/nickel-thiacalix[4]arene coordination compounds were obtained with p-tert-butylthiacalix[4]arene(H4TC4A)as the terminal ligand and polyazoles as the bridges under solvothermal conditions.The effect of the structures and coordination modes of the polyazole ligands and counter inorganic ions in the reaction system on the formation of the products was investigated.The catalytic properties,magnetism and adsorption behavior of these compounds were studied.In addition,a chiral coordination cage which can separate L-serine and D-serine was obtained with chiral malic acid as the linker.The main work is as follows:1.Compounds 1-4 were obtained by introducing a diazole ligand,2,5-dihydro-1,3,4-thiadiazole-2,5-dithiol(L1)into the nickel-H4TC4A system.It is found that the in-situ generated CO32-anion and the added SO42-anion are crucial to the formation of{Ni20},{Ni24} and {Ni32}.An isolated hinged double-dumbbell-like {Ni8} cluster(1)which is constructed by two Ni4-(TC4A)2 SBUs through one L1 ligand was obtained using NiCl2 as the metal precursor.When DMF was introduced into the reaction system to in-situ generate some CO32-anions,a twisted double-bowl-shaped {Ni32}cluster(2)was obtained with the shuttlecock-like Ni4-TC4A SBUs as the nodes.When SO42-anion was introduced into the reaction system and there was no in-situ generated CO32-anion,a wheel-like {Ni20} cluster(3)formed.When a small amount of DMF and a large amount of SO4-anions were added to the reaction system simultaneously,all SO42-anions bonding the lower rim of the coordination wheel of compound 3 would be replaced by CO32-anions,and the bottom of the wheel was capped by another Ni4-TC4A SBU,thus a bowl-shaped compound {Ni24}(4)formed.The catalytic performance of compounds 1-4 for glucose oxidation in alkaline solution were studied and compound 3 is a good catalyst for glucose oxidation.Its performance is better than that of some non-noble metal materials.[Nig(TC4A)4L1]2-(1)[Ni32(TC4A)8(L1)8(CO3)4(HCOO)2Cl8]2-(2)[Ni20(TC4A)5(L1)5(SO4)5Cl5]5-(3)[Ni24(TC4A)6(L1)5(CO3)5(SO4)(HCOO)Cl5]4-(4)2.By choosing triazole ligand having three N atoms,1H-1,2,3-triazole-4.5-dicarboxylic acid(L2),as the bridging ligand,an octahedral {Co24} coordination cage(5),a double-dumbbell-like cluster {Co8}(6),a three-dumbbell-like cluster{Co13}(7)and another double-dumbbell-like cluster {Ni8}(8)were obtained.Compounds 5-8 have good selectivity for the adsorption of mercury ion and compound 5 is the best with the saturated adsorption capacity towards mercury ion being of 330 mg·g-1.[Co24(TC4A)6(L2)6(SO4)6(HCOO)6]6-(5)[Co8(TC4A)4L2]3-(6)[Co13(TC4A)6(L2)2]4-(7)[Ni8(TC4A)4L2]3-(8)3.By choosing triazole ligand,5-(4-pyridyl)-1H-1,2,4-triazole-3-thiol(L3),as the bridging ligand,two one-dimensional compounds {Co4}n(9)and {Co8}n(10)were obtained.That is,when several drops of triethylamine were added into the reaction system,a wavy one-dimensional compound 9 formed,while a different one-dimensional compound 10 was obtained with a few drops of concentrated hydrochloric acid added into the reaction system.The adsorption capacity and mechanism towards Hg(?)by compounds 9 and 10 were studied,and the adsorption capacity of compound 9 was better than that of compound 10.{[Co4(TC4A)(L3)2(SO4)2]2-}n(9){[Co8(TC4A)2(L3)2(SO4)3(CH3OH)6]}n(10)4.When a tetrazole ligand,5-mercapto-1-methyltetrazole(L4)was chosen as the bridging ligand,four {Co4}/{Ni4} compounds(11-14)were obtained using different metal salts as the metal precursor under the same solvothermal condition.Magnetic measurements reveal that all the metal centers of compounds 11-14 exhibit antiferromagnetic interactions.[Ni4(TC4A)Cl(L4)4]-(11)[Co4(TC4A)Cl(L4)4]-(12)[Ni4(TC4A)(SO4)(L4)3(CH3OH)]-(13)[Co4(TC4A)(SO4)(L4)2(CH3OH)2.5(H2O)1.5](14)5.A chiral {Co24} coordination cage(15)was obtained using chiral linear L-(-)-malic acid(L5)as the bridging ligand under solvothermal condition.In the structure,twelve L5 ligands act as the edges to connect six Co4-TC4A SBUs to form an octahedral coordination cage.Compound 15 can effectively recognize L-serine and D-serine.[Co24(TC4A)6Cl6(L5)12]6-(15)...