Synthesis, Structures And Properties Of Lanthanide Coordinate Polymers Based On N/O Ligand

In the last few decades, lanthanide complexes have attractedmuch attention due to their photoluminescent properties, in recentyears, many researches have been carried out onlanthanide–transition metal (4f–3d) heterobimetallic compoundsbecause of their potential application as functional materials inheterogeneous catalysis, luminescence and magnetism. Accordingto HSAB theory, ligands posseing N/O donor are adsvantage toconstruct4f-3d heterobimetallic compounds. Here,4-(imidazol-1-yl)-benzoic acid (Himba) was selected to constructlanthanide coordination polymers. This dissertation consists of fivechapters.In chapter1, HSAB (Hard-Soft-Acid-Base) theory, recent advanceson syntheses, structures, properties of lanthanide MOFs and3d-4fheterometallic complexes were introduced briefly.Chapter2: Four isostructural heterometallic complexes have beenobtained, namely [LnCu2(imba)4(CuI2)](Ln=Dy, Tb, Eu, Gd, for1-4), byuseing4-(imidazol-1-yl)-benzoic acid (Himba). SEM-EDS werecarried out to ensure the heterometal doped. In compounds1-4, Cu1and Ln(III) are connected with each other by 4-(imidazol-1-yl)-benzoic to form a1D ribbon, Cu2is coordinatedwith iodine atoms to form a [CuI2] chain. The two isolated1Dribbons and [CuI2] chain are connected by weak Cu-Cu interactionto form3D framework. Photoluminecence of compound3wasimpossible because of the dark crystals colour. But, the colour haschanged (black to grey) when soaking in NaClO4(aq). Luminescenceof compound3couled be contributed toTb[620nm(5D4�'7F3),584nm(5D4�'7F4),540nm、548nm(5D4�'7F5),492nm、488nm(5D4�'7F6)].Chapter3: Seven compounds were synthesized successfully byusing oxalate as auxiliary ligand, namely [Ln2(ox)3(Himba)2](Ln=Dyfor7, Ln=Er for8),[Gd(ox)(H2ox)(Himba)(H2O)](9) and [Tb1-xEux(ox)(H2ox)(Himba)(H2O)](x=x=0,0.16,0.071,0.037, for10,11,12,13, respectively). Interestinly, rational doped Tb3+and Eu3+insyntheses have carried out to series of isostructural compounds10-13, which tuned the luminescence colors from green to red, toreddish orange, to orange.Chapter4: Isostructural Cu/Zn doped metal-organic framework havebeen documented, namely [Cu2-xZnx(ina)3(COOH)(H2O)](x=0,0.392，for14,15respectively), which have been ensured by SEM-EDS. Twoadjacent Cu2atoms connected by carboxylates forming apaddlewheel, which was further linked by Cu1and ina generating afive-connected2D layers. Adjacent layers were three-foldinterpenetrated to form a3D framework. Solid state UV-Vis charactershowed that the Eg values are3.50eV and3.44eV respectively.