Synthesis, Structure, Photoluminescence And Thermal Properties Of Cu～Ⅰ/Cu～Ⅱ/Zn～Ⅱ Metal Coordination Polymers Based On Bis(Imidazol-1-yl-methyl) Benzene

The work under this title focuses on the design and synthesis of twelve new functionlized Cu^â… /Cu^â…¡/Zn^â…¡complexes. Solvothemal or ambient layer diffusion reactions of imidazole-based ligands with metal ions under varied temperatures, stoichiometries and in different solvents afforded the complexes in 1D, 2D and 3D frameworks. To probe the effect of construction on the bulk property of MOFs, the solid properties of the coordination polymers, including crystal structure, thermal decomposition and room temperature photoluminescence have been studied. The lab outcomes show that prediction of MOFs on basis of mere information of building blocks is badly difficult and even impossible because the structure of MOF depends not only on the constitutional factors, but also the non-constitutional, such as temperature, pressure, pH value, ratio of metal-ligand, solvent polarity and co-existing non-coordinative species, etc. On the other hand, it is proved also that one can control the dimension of MOF by choosing geometrically appropriate ligands. More than that, the results reveal that the bulk performance of the MOFs is subject to their micro-organization of MOE Therefore, it is possible for us to tune the function of hybride solids through modifying their structures. In the following, we'll elucidate the structural and functional details of these compounds. The thesis is divided into three chapters.In the first chapter, a brief survey of the coordination polymer chemistry is presented. Some concepts and significance of this area are described. Especially, the synthetic teetic and potential applications of metal-organic frameworks are intentionally stressed. In relevance to the present research, the intriguing topologic features of coordination polymers derived from these flexible N-functiomalized imidazole ligands are illustrated. On basis of the background, we explained the reason why we choose this topic as my interest.In the second chapter, six new structurally-fascinating polymers, [(Cu₄I₄)(p-BIMB)₂]_n (1), [Cu^â…¡(p-BIMB)_0.5Br]_n (2), [Cu₂^â…¡(p-BIMB)Cl₂]_n (3), [Cu₂^â…¡(p-BIMB)(CN)₂]_n (4), [Cu₂^â…¡(o-BIMB) (CN)₂]_n (5), [Cu₂^â…¡(o-BIMB)(SCN)₂]_n (6), which are synthesized from solvothermal reactions of CuX with imidazole-based ligands, are involved. These compounds have been characterized by IR spectra, elemental analysis and X-ray crystallography. Their crystal structures show that the six complexes possess an increasing dimensionlity from 1-D(3) to 2-D(1-2, 5-6) to 3-D(4), which indicates the isomer ligands with different endo-cis and endo-anti conformations take essential role on the framework of the Cu^â… coordination polymers. Lastly, the photoluminescenee and thermal properties of six complexes have been studied.Likewise, the third chapter includes six novel complexes derived from imidazole-based ligands and Cu^â…¡/Zn^â…¡. Four Cu^â…¡coordination polymers , {[Cu^â…¡(p-BIMB)₂](SCN)₂(H₂O)₂}_n(7), [Cu^â…¡(o-BIMB)₂(SCN)₂]_n (8), {[Cu^â…¡(p-BIMB)₂](N₃)₂(H₂O)}_n (9), {[Cu^â…¡(o-BIMB)₂](N₃)₂}_n(10), were synthesized via ambient layer diffusions; two Zn^â…¡polymers, [Zn^â…¡(p-BIMB)(SO₄)]_n (11), [Zn_0.5^â…¡(o-BIMB)(ClO₄)]_n (12) were obtained solvothermally. Comparisons of 7 with 8 and 9 with 10 discovered that solvent plays a role in the construction of MOF; Further, the comparison of 7 with 9 and 8 with 10 reveals that anion does not affect the assembly of BIMB ligands with Cun ion. More of interest is that the p-BIMB-derived 7 and 9 are 1D higher than the comparably isolated o-BIMB derived 8 and 10, respectively, reifying the influence of ligand geometry on dimension of MOF.