【作者】 侯芹；

【导师】 徐家宁； 于杰辉；

【作者基本信息】 吉林大学 ， 无机化学， 2010， 博士

【摘要】 本论文主要从事金属-卤素簇合物的合成、结构和性能研究。利用水热(溶剂热)合成方法选用不同的含氮杂环脂肪胺和芳香胺与Cu(I)-X,Pb-X和其它金属(Co, Ni, Cd)-X合成了二十个金属-卤素簇合物,其中十九个为新化合物。1.采用不同尺寸大小的含氮杂环脂肪族二胺合成了五个新的Cu(I)-I簇合物。化合物1是由哌嗪桥联一维具有类城墙结构的Cu2I2双链而成的三维结构的化合物。化合物2是由1D类城墙双链和1D环形链通过共用Cu-I二聚体而成的二维层状化合物。以Cu4I4簇为次级建筑单元构筑了具有二重互穿quartz拓扑的化合物3和具有五重互穿的类金刚石结构的化合物4。化合物5是由双质子化的bpp分子与孤立的[Cu2I5]3-阴离子簇形成的具有三维超分子网络的化合物。2.通过水热(溶剂热)配体原位生成反应得到六个化合物。化合物6是以Cu6I6和Cu8I8簇单元为节点构筑的具有sqp拓扑的三维结构。化合物7是由2-COOpy配体桥联金属铜而形成的链状的配合物。化合物8中展现了一个少见的[Cu3I4]-阴离子层。化合物9, 10, 11中分别存在一维[Cu2I3]-链,一维[Cu2I4]2-链和孤立的[Cu4I6]2-簇,并通过C?H???I氢键相互作用形成三维的超分子网络。3.由含氮杂环脂肪二胺及其衍生物为模板合成了五个铅卤酸盐。化合物12是第一例具有孔状接缝的二维层状的铅碘酸盐。以质子化的三乙烯二胺为模板剂构筑了一维链状的铅碘酸盐13和一维双链结构的铅溴酸盐14。化合物15中的[Pb2I6]2-阴离子具有一维带状结构。化合物16中的[Pb2I6]2-阴离子与化合物14中的[Pb2Br6]2-是同构的。4.利用哌嗪和不同的MX2(M= Co, Ni, Cd; X= Cl, Br, I)合成的四个具有不同维数的化合物17-20。5.考察了有机配体、反应体系的pH值等因素对反应产物的影响。对所合成的化合物进行了多种谱学表征,对部分反应可能的反应机理和荧光进行了初步研究,为进一步探索化合物功能特性和结构的关系提供物质基础。更多还原

【Abstract】 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.更多还原