| The study on the novel halogenated metal coordination polymers is of current hot topic in the field of inorganic chemistry due to the fascinating structures and the potential applications in the areas of optics, electrochemistry, magnetism, host-guest chemistry and metallic conductivity. One of the hot topics in halogenated metal coordination polymer is the construction of the coordination polymers based on halogenated metal clusters as the Second Building Units(SBUs). The introduction of the halogenated metal clusters not only can keep their inherent properties, but also can obtain novel compounds with novel structures and functions.Based on this mechanism, we synthesized 20 metal-halo coordination polymers based on aliphatic N-heterocyclic diamines, aromatic amines and Cu(I)-X, Pb-X, (Co, Ni, Cd)-X in hydro(solvo)thermal conditions. We discussed the influence of the form, size of the organic ligands and solvent, pH and temperature etc. On the bases of X-ray structural analyses, compounds have been characterized by IR, UV, fluorescence spectra and thermal analyses, which would play an important role in exploration of the structures and functions for coordination polymers. This thesis is divided into seven chapters.In the first chapter, we concisely introduced the histories of metal-halo clusters and emphasized the developments of copper(I) halides and haloplumbates as well as the hydro(solvo)thermal in situ ligand syntheses. At the end of this chapter, we pointed out the research significance and the results in this thesis.In the second chapter, the principle, methods and the reagent used in the syntheses are summarized by the large.In the third chapter, five new Cu(I)-I cluster coordination polymers based on aliphatic N-heterocyclic diamines with different sizes in solvothermal conditions have been prapared. They are [Cu2I2(pip)] (1),[Hpip][Cu3I4] (2),[Cu4I4(dach)2] (3),[Cu4I4(bpp)2] (4) , [(H2bpp)2][Cu2I5]I·2H2O (5) (pip = piperazine, dach = 1,4-Diazacycloheptane, bpp = 1,3-bi(4-piperidyl)propane ). Compound 1 features a new 3-D framework constructed from 1-D merlon-like CuI double chains by pip bridges. It is interesting that, this 3-D framework exhibits 1-D channels in different directions. In [100] direction, the channel is rectangular with the size of 2.7×9.0 ?2, whereas in [001] direction the channel is a diamondoid structure with the size of 7.5×13.9 ?2. Compound 2 features a 2-D layer, which constructed from 1D merlon-like CuI double chains and 1D loop chains by sharing Cu-I dimers. Pip molecules adopt monoprotonated style, with one side coordinated with Cu atoms and the other side protonated to balance the charges of the framework. Pip molecules protrude out from 1D merlon-like CuI double chains, extending along the c axis. Compound 3 displays a 3-D two-fold interpenetrated framework built up from Cu4I4 clusters by dach bridges. From the topological point of view, the 3D framework in 3 is a quartz structure, to our knowledge, it is the fourth member of rare 3D frameworks with a quartz-like topology. It is interesting that, compound 3 exhibits two kinds of channel in ab plane: with the size of 8.72×11.22 ?2 and 14.9×18.12 ?2; two kinds of channel in bc plane with the size of 8.31×18.12 ?2 and 15.03×15.18 ?2, respectively. Using the longer ligand bpp molecules, compound 4 exhibits a diamond-like topology with 5-fold interpenetrated based on Cu4I4 clusters as nodes. Compound 5 features a 3-D supramolecular framework, which constructed from diprotonated bpp molecules and discrete [Cu2I5]3- clusters by hydrogen bondings.Aliphatic N-heterocyclic diamines with different styles exist in compounds 1-5: bi-bridged in compounds 1, 3 and 4; Mono-bridged and the other side protonated in compound 2; As the templates to banlance charges in compound 5. pH values play an important role in constructing compounds 4 and 5. The X-ray single crystal analyses, elemental analysis, IR and TG have been performed on these compounds. Compounds 1-5 possess good fluorescence emissions.In the fourth chapter, six new coordination compounds prepared through in situ ligand syntheses: [Cu14I14 (dabco)5(py)] (6) , [Cu(2-COOpy)2]·H2O (7) ,[N-C2H5py][Cu3I4] (8),[N-CH3py][Cu2I3] (9),[N, N, N', N'- (CH3)4pip][Cu2I4] (10), [(N-CH3dabco)2][Cu4I6] (11) (dabco = dabco = 1,4-diazabicyclo[2.2.2]octane, py = pyridine, 2-COOpy = 2-carboxylpyridine, N-C2H5py = N-ethylpyridine, N-CH3py = N-methylpyridine), have been in detail described. Full-decarboxylation reaction and semi-decarboxylation reaction of pyridinedicarboxylic acid were detected in compounds 6 and 7. N-C2H5py in 8 and N-CH3py in 9 derived from the solvothermal in situ simultaneous decarboxylation and N-alkylation reactions of 2,5-(COOH)2py. With Cu6I6 and Cu8I8 clusters as 5-connected nodes, compound 6 features a new 3-D network sqp topology. The two-fold interpenetrated framework is generated by accommodating two identical sqp networks by inversion center. Compound 6 is the first example of interpenetrated sqp net with covalent bonds. Compound 7 is a 2-COOpy-bridged chained Cu coordination polymer. The lattice water molecules link to each other to form a 1-D zigzag-type water chain through the O?H???O hydrogen bondings, extending along the a axis. These two kinds of chain further linked into 3D supramolecular network through O(C)?H???O hydrogen bondings. Comound 8 exhibits a rare [Cu3I4]- 2D layer, which further extended into 3D supramolecular network throgh C?H???I hydrogen bondings. The basic building block of [Cu3I4]- layer is [Cu2.5I2]0.5+ subunit. Compound 9 consists of the [N-CH3py]+ cation and the 1-D [Cu2I3]- chain. Compound 10 is constructed by [Cu2I4]2- chain and N-alkylated piperazine, which further extended into 3D supramolecular network through C?H???I hydrogen bondings. In compound 11, mono-alkylated dabco molecules were detected and coordinated with Cu molecule as terminal ligand.In the fifth chapter, applying in hydro(solvo)thermal synthesis reactions, five new organically templated haloplumbates: [H2dabco][Pb3I8] (12), [Hdabco] [PbI3]·H2O (13), [H2dabco][Pb2Br6]·H2O (14), [H2depip][Pb2I6]·H2O (15), [H2dppip][Pb2I6]·H2O (16), have been in detail described. compound 12 is the first example of 2-D layered iodoplumbate with perforated structure. The subunit of the perforated layer is a serrated [Pb3I8]2- ribbon, consisting of four infinite chains of edge-shared octahedra featuring the excision of some PbI+ moieties on both side-chains of the ribbon. Templated by monoprotonated dabco, threeμ2-I- ions bridge the Pb(II) octahedra into a 1-D chain structure iodoplumbate of compound 13. Templated by diprotonated dabco, PbBr2 is transformed into a 1-D double-chain structure bromoplumbate of compound 14 based on the Pb2Br9 subunits. The [Pb2I6]2- anion in compound 15 possesses the 1-D ribbon structure, in which the repeat subunit is a planar bi-bridged tetramer. It is interesting that the 1-D ribbons are self-assembled into a 2-D supramolecular layer via the weak inter-ribbon I···I interactions. The [Pb2I6]2- anion in compound 16 is isostructural with that of [Pb2Br6]2- in compound 14.The solvothermal in situ N-alkylation reactions (15, 16)of pip with alcohol solvents in the present of I- at acidic conditions provide a new approach to obtain a series of new organic templating agents.In the sixth chapter, four 1:1 adducts of MX2 and piperazine: [CoCl2(pip)] (17), [NiCl2(pip)] (18),[CdBr2(pip)] (19), [CdI2(pip)] (20) were obtained. Compound 17 exihibits a 1D zigzag chain, in which Co atoms with tetrahedral geometry. In compounds 18-20, MX2 features a 1D linear chain, for M(pip)22+ unit, the cis-type arrangement corresponds to the 3D network(18, 19), while the trans-mode configuration leads to the 2D sheet(20). In addition, variable-temperature magnetic susceptibility measurements for compound 18 indicate that it displays ferromagnetic interaction during 14-300K, whereas the drop below 14 K can be related to antiferromagnetic coupling between the chains as well as the effect of zero-field splitting.In the seventh chapter, a brief conclusion and outlook of this thesis are given.
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