Study On The Self-Assembly, Characterization And Properties Of Supramolecular Complexe Based On Nitrogen-Containing Heterocyclic

Nitrogen-containing heterocyclic and its derivatives include imidazole, quinoline, pyridine and pyrazine, because the diversity of coordination model, they often form supramolecular complexes with transition metal by self-assembly, and these complexes have shown unique optical, magnetic, electrical, and biological nature. Therefore, the design, synthesis and characterization of these complexes have been the research hotspots. In this thesis, we had designed and synthesised a series of complexes containing nitrogen-containing heterocyclic, described their structures determined by X-diflfraction method, and studied their electrochemical properties, third-order nonlinear optical properties and fluorescence properties.We had used three imidazole derivatives including 1-allyl-1H-imidazole (Aim), benzimidazole (Bim),1-benzylimidazole (Blim) as a ligand, and KSCN as the structure construction unit, with different metal ions to assemble six mononuclear complexes.Cu(Aim)2(SCN)2, Ni(Aim)4(SCN)2, Mn(Aim)4(SCN)2, Cu(BIim)3(SCN)2, Co(Blim)4(SCN)2,Ni(Bim)4(SCN)2, then we had described their structures determined by X-diffraction method, and studied their electrochemical properties by cyclic voltammertric approach.[M(μ4-pz25dc)]n (M=Cd or Zn) had been synthesized by 2,5-pyrazine dicarboxy-lic acid ligand and Cd2+, Zn2+, [Cu(PPh3)2Him]Br had been synthesized by triphenylphosphine (PPh3) and 1-H-imidazole (Him) ligands with Cu2+ for self-assembly. We had described their structures determined by X-diffraction method, and studied third-order nonlinear optical properties. Herein, we had reported the use of [V4O]2]4- cyclic cluster as an architectural motif and geometric constraint ligands to construct three related cluster polymers{[V4O12Cu2(vim)4]·H2O}, {[V4Oi2Cu2(py)8]-2H2O}n, and [V4O12Cu2(pyz)]n(vim=N-vinylimidazole, py= pyridine, pyz= pyrazine), and we had described their structures determined by X-diffraction method, and their third-order nonlinear optical properties.The new bidentate ligand of benzimidazole derivative N-methyl-lH-benzimidazole-2-carboxamide (MBF) was synthesized. The assembly of MBF with transition metal ions Cu2+、Ni2+、Cd2+、Co2+ afforded ML2 mononuclear complexes. The MBF ligand afforded 2 coordination sites and chelated metal ions to form five-number ring with bidentate mode. [Cu(MBF)2](NO3)、[Cu(MBF)2](Cl)2、[Ni(MBF)2](NO3). [Co(MBF)2(H2O)2](NO3)2 have been synthesized. The UV-Vis spectra and electro-chemical properties of the complexes were investigated.A new ligand (E)-2-(4-(diphenylamine)styrene)-8-hydroxyquinoline (DPSQ) was synthesized by triphenylamine and 8-hydroxyquinoline, then we had synthesized four rare earth metal complexes, including Eu(DPSQ)3·H2O, Sm(DPSQ)3·H2O. Tb(DPSQ)3·H2O, Dy(DPSQ)3·H2O.We determined the complex structure and composition by elemental analysis, infrared spectroscopy and nuclear magnetic resonance spectroscopy. Absorption spectra measured by UV-vis absorption peaks of the four kinds of rare earth metal complexes, and fluorescence spectroscopy.