Design And Syntheses Of Some Functional Coordination Polymers With N Ligands And In Situ Reation

Metal-organic coordination polymers have a wide range of applications, due to their special properties in magnetic, optics, electronics, absorption and catalysis etc. Their highly order structures via coordinative bonds, hydrogen bonds and Ï€-Ï€ interactions have been extensively explored, They present not only novel structures with special properties, but also the knowledge to understand how the novel structures are formed, so the complexes with specific properties can been designed and synthesized.In this dissertation, several nitrogen heterocyclic carboxylate ligands were selected as the basic constructing units, and 14 novel coordination polymers were synthesized via hydro(solvo)thermal reactions. They are [Zn(ip)(4,4-bipy)₂][Zn(ip)(4,4-bipy)]_n .0.25nH₂O (1), [Co₂(C₁₃H₁₄N₂)₂(C₁₀H₈O₆)₂H₂O]_n (2), [Zn(C₁₃H₁₄N₂)(C₁₀H₈O₆)0.5H₂O]_n (3), [Zn(C₁₃H₁₄N₂)(C₈H₄O₄)]n .n0.5H₂O,(4) ,[Zn₂(C₁₃H₁₄N₂)(C₈H₄O₄)₂]_n (5) ,[Co(C₈NH₆O₄)₂]_n.3nH₂O (6) , (Co(C₈NH₅O₄)(H₂O)]_n,(7),[Zn(C₈NH₅O₄)(C₁₀N₂H₅ )_0.5(H₂O)]_n.n1.75(H₂O) (8), [Cu₂Cl₂(C₂₆H₂₂N₄O)]_n (9), [Cu₆I₆(C₂₆H₂₂N₄O)( C₁₃H₁₄N₂)₄]n (10), (C₈H₆O₄) (11), (C₁₄H₁₀O₄S) (12),[Mn_0.5(C₈H₈O₂)(C₁₂H₈N₂)_0.5]_n (13) , [Mn(C₈H₈O₂)₂(C₁₂H₈N₂)0.5(H₂O)] ( 14 ) å’Œ [Zn(C₇H₄O₂S) (C₁₂H₈N₂)] (15) .All of them have been characterized by X-ray single-crystal diffraction, IR spectrum, element analysis. Some of these compounds have been discussed with their magnetic, photoluminescent, TG and powder XRD measurement results.Complex 1 has a rare "2D+2D" parallel array structural motif and complex 2 and 3 are three-dimensional (3D) supramolecular polymers with double-helical chains. Complex 4 has a 4-fold diamondoid architecture and complex 5 forms a NaCl-type topological structure through 2-fold interpenetration. Complex 6 has a porous framework self-assembled through metal-organic coordination interactions as well as strong H-bond interactions with water molecules inside the porous as guests. Complex 7 has a (4.6²)₂ (4². 6¹⁰ . 8³ ) topological structure while complex 8 has layer-like porous architecture and further extended into a 3D network via H-bond interactions with water molecules inside the porous as guests. In complex 9 and 10, the N-heterocyclic ligand (BPP) have undergone an in situ dehydrogenative coupling reaction as well as hydroxylation to lead to the new ligand, l-hydroxy-l,2,4,5-tetrakis(4-pyridyl)cyclohexane. The new ligand are assembly with copper(I) halides to form 1D infinite chain and 3D architecture, respectively. In Complex 11, decarboxylation reaction wasobserved and the Rjbtc Hgand was converted in situ into terephthalic acid by loss of two carboxyl groups. Then terephthalic acid with BPP ligand to give rise to a OD structural motif and further extended to a 3D coordination framework via H-bond interactions. Complex 12 was obtained as a result of the desulfurization of the thiosalicylic acid Hgand., In complex 13 and 14, KMnO4 has undergone a deoxidize reaction firstly and self-assembly with 1,10-phen to form OD structure and further extended to the 3D architectures via 7i-7t interactions. In complex 15, has undergone a deoxidize reaction firstly in situ into thiosalicylic acid ligand and self-assembly with zinc and 1,10-phen to form OD structure and further extended to the ID architectures via n-n interactions.