Coordination Complexes Based On Aromatic Polycarboxylates Or Polyoxometalates: Syntheses,Structures And Properties

The main objective of this thesis is to design and investigate novelorganic-inorganic compounds, based on aromatic polycarboxylates orpolyoxometalates, which have been synthesized by hydrothermal synthesis method.The influences of reaction conditions and the mechanisms of synthesizing processwere investigated. The properties of these compounds were studied. Thesecompounds have been structurally characterized by single crystal X-ray diffractions,elemental analyses, IR and TG. The fluorescent activities of these compounds havealso been studied?1. Seven three dimensional (3D) lanthanides compounds were hydrothermallysynthesized based on H4bta as an organic unit. Compounds5and6are composed oftwo dimensional (2D) metal-oxygen layers, and compound7contains onedimensional (1D) metal-oxygen chain. Three new coordination modes of H4bta arereported for the first time.[Pr(bta)0.5(H2bta)0.5(H2O)](1)[Eu2(bta)1.5(H2O)2](2)[Ln2(bta)1.5(H2O)4]3H2O (Ln=La(3), Ce(4))[Ln2(bta)1.5(H2O)2] H2O (Ln=Ce(5), Pr(6))[Pr(bta)0.5(H2bta)0.5]5H2O (7)2. Eight novel compounds were synthesized with in situ amidation hydrothermalreactions of aromatic polycarboxylates and hydrazine. H4bbch was firstly obtainedwith reaction of H4bta and hydrazine with a starting ratio of1:1.[Cu(H3bbch)(H2O)]2·2H2O (8)[Fe3(Hbbch)2(H2O)2(H2O)2]·2H2O (9)[Zn(H2bbh)(N2H4)1/2(H2O)]·2H2O (10)[Cd(H2bch)2(2,2'-bpy)(H2O)2][Cd(H2bch)(2,2'-bpy)(H2O)2](H2bch)(11)[Cd2(Hbch)2(phen)2]·H2O (12)[Zn2(Hbch)2(phen)2]·H2O (13)[Zn(Hbch)(2,2'-bpy)](14)[Cd(bta)1/2(N2H4)(H2O)]·H2O (15)3. With utilization of4,4'-bipyridine (bipy) organic template, six Keggin-typepolyoxometalates based compounds were synthesized. In addition, two compoundsbased on Keggin-type polyoxometalates includes1,10-phenanthroline (phen) and 1,6-bis(imidazole-1-yl)hexane (bbi), respectively, have also been obtained. In thesynthesizing process, pH and La(NO3)3are the crucial issue for the final structures ofcompounds16-21.(SiMo12O40)(H2bipy)2·2H2O (16)[Cu(Hbipy)4(HSiMo12O40)(SiMo12O40)](H2bipy)0.5·7H2O (17)[Cu2(Hbipy)6(bipy)(SiMo12O40)3](Hbipy)2·6H2O (18)[Cu2(bipy)2(SiMo12O40)](H2bipy)·2H2O (19)[Cu2(bipy)4(H2O)4](SiMo12O40)·13H2O (20)[Cu(bipy)]2(SiMo12O40)(H2bipy)·2H2O (21)[SiMo12O40](H2bbi)2·2H2O (22)[Cu2(phen)4(SiMo12O40)](23)(H4bta=benzene-1,2,4,5-tetracarboxylic acid; H4bbch=benzene-4,5-bicarboxylate-1,2-hydrazide; H4bbh=benzene-1,2,4,5-bihydrazide;H3bch=benzene-4-carboxylate-1,2-hydrazide;2,2'-bpy=2,2'-bipyridine; phen=1,10-phenanthroline; bipy=4,4'-bipyridine; bbi=1,6-bis(imidazole-1-yl)hexane)...