Syntheses, Structures And Properties Of Coordination Polymers With Dinitronaphthalenedicarboxylate And Biphenyltetracarboxylate

Many coordination polymers have been synthesized, providing a variety of properties such as porous materials, catalysis, optical properties, magnetism, and drug storage and delivery, etc, which are one of current research focus of chemistry, material and life science fields. The organic ligands containing two or more carboxylate groups offer great potentials for fine control over coordination architectures. Under the guidance of crystal engineering, 1,5-dinitronaphthalene-3,7-dicarboxylate and 2.2',4.4'-biphenyltetracarboxylate are used as bridging ligands between metal ions, in combination with pyridyl ligands and 1,1O-phenanthroline(phen) as auxiliary bridging ligands or terminal ligands. Thirty-two new coordination compounds, including zero dimensional, one dimensional, two dimensional, and three dimensional structures, have been prepared, and the magnetic properties, thermostability and solid-state luminescence properties of some compounds have been characterized. This dissertation covers the following two parts:1. Coordination compounds of 1,5-dinitronaphthalene-3,7-dicarboxylateHydro(solvo)thermal reactions of 1.5-dinitronaphthalene-3,7-dicarboxylate (H2NNDC) and metal ions or in the presence of a series of systematically varied bridging and terminal ligands (L′(?) 4,4'-bipyridine, bpe, dabco, phen) afford twenty-five coordination compounds. X-ray analyses reveal the structures of these compounds, whose stability, guest-inclusion properties of the porous materials, magnetic properties and luminescence also have been characterized.(1) Hydro(solvo)thermal reactions of H2NNDC and metal ions M(Ⅱ) (M= Co Ni Cu and Mn) afford series different structures. Compound 1 is zero dimensional structure, which is generated to 3D net by extensive hydrogen bonding andπ-πinteractions. Magnetic analysis on the compound 1 revealed a ferromagnetic intra dimer interaction through the mixed aqua and carboxylate bridges. Similar to compound 1, compound 2 is also generated to a 3D architecture with theα-Po topology by hydrogen bonds. The structure 3 consists of one-dimensional chains. which are associated into 3D ladder-like nets through hydrogen bonds andπ-πinteractions. The compound 4 exhibits a 3D framework with the pcu topology. magnetic analyses suggest relatively weak antiferromagnetic interactions within the carboxylate bridged [Mn3(COO)6] cluster of 4.(2) Hydrothermal reactions of H2NNDC and Ni(Ⅱ) in the presence of bis(4-pyridyl) ligands afforded two isomorphous 3D coordination networks (5.6). The flexibility of the 3D mother framework [Ni(NNDC)]n derived from Ni(Ⅱ) and NNDC ligand allows for the incorporation of different second bridges, and the resulting materials can be a metamagnet or a paramagnet depending upon the length of the second bridge. This is a novel case of magnetic modulation by varying the corporate bridging ligand accommodated in a flexible mother framework, and may open a new approach of modulating the properties of magnetic MOF materials.(3) Hydrothermal reactions of H2NNDC and Co(Ⅱ) in the presence of auxiliary ligands(4,4'-bipy, bpe, phen) afforded three 3D coordination compounds(7-9). compound 9 is rare 3D structure. The flexibility of the 3D mother frameworks([Co(NNDC)]n) derived from Co(Ⅱ) and NNDC ligand allows for the incorporation of different corporate bridges, variable-temperature magnetic susceptibility measurements indicate the presence of antiferromagnetic in the syn-syn Co(II)-carboxylate chains of 9, while ferromagnetic interaction in the syn-anti Co(II)-carboxylate chains of 7,8.(4) Hydrothermal or diffusion reaction of H2NNDC and Ni(Ⅱ),Mn(Ⅱ) in the presence of other corporate ligands (phen and bpe) afforded coordination compounds(10-13). Hydrothermal reactions of H2NNDC and Ni(Ⅱ) in the presence of 1.10-phen afforded two same composition coordination compounds(11.12). they are zero dimensional motif and 1D chains, respectively. The magnetic properties of Ni(Ⅱ) compound 12 are characterized, which have rich water bridges, ferromagnetic interaction in 12.(5) Crystal engineering of coordination polymers with H2NNDC and bipyridyl/chelating ligands:series of novel ID.2D and 3D coordination compounds with Zn(II) and Cd(Ⅱ) have been synthesized and structurally characterized by single crystal X-ray diffraction. Compound 17 is based on paddle dinuclear zinc(Ⅱ) SBU that linked via NNDC and dabco liuands to form 3D structure. The framework stability of some polymers has been investigated. (6) Solvothermal reactions of H2NNDC and Ln(Ⅲ) (Ln= La,Nd,Eu,Gd,Tb and Yb) afford six coordination polymers. X-ray analyses reveal the structures of these compounds are isomophous 3D lanthanide metal-organic frameworks based on dinuclear Ln(Ⅲ) SBUs, and they are default primitive cubic (pcu) net. The framework stability of the polymers has been investigated. The Eu(Ⅲ) compound(22) displays intense luminescence as a result of the efficient ligand-to-metal energy transfer.2. Coordination polymers tuned by 2,2',4,4'-biphenyltetracarboxylate (2,2',4, 4'-H4bptc)Hydrothermal reactions of 2.2'.4,4'-H4bptc and M(Ⅱ) (M= Co and Cu) afford seven coordination polymers. X-ray analyses reveal these compounds are only one 2D and six 3D structures, respectively. Antiferromagnetic interaction in alternate Co(Ⅱ) chains of compound 27. The compound 29 is typical antiferromagnetic exchange. While variable-temperature magnetic susceptibility measurements for compound 28 indicate the presence of ferromagnetic in the Cu(Ⅱ)-carboxylate chains. With topology analyses, the same"Ⅱ"organic building block and 6(4)-SBUs are included in the structures of the compound 29 and 30-32. In compounds 30-32, The 3D mother framework [Cu2(2,2',4,4'-bptc)]n derived from Cu(Ⅱ) and bptc4- allows for the incorporation of different auxiliary ligands. which never have been reported to our knowledge. The auxiliary bridging or terminal ligands can be selectively included in the compounds 30-32. provided that the specific size and shape of the liagnds well match the"pore"of the framework in size and metal-site arrangement.