Tetrapod-like zinc oxide whisker （T-ZnOw） is one kind of multifunctional inorganic material with uniform three-dimensional structure. High pure zinc powders are unreasonably demanded in the present production techniques and fussy processing of zinc powder is a prerequisite in some cases. So the mass production is difficult to achieve and higher costs hinder its further application in many fields. From these considerations, this study explored the optimum process conditions of preparing T-ZnOw by direct oxidation of non high-grade Zn powders at ambient pressure on the basis of in-depth study of the theory of nucleation and growth. The effects of aluminum doping on the electrical resistivity of T-ZnOw were investigated. T-ZnOw doped with gallium was prepared and it had good electric conductivity preformance.In this thesis, many factors having the impact on whiskers size, shape and yield were studied systematically in synthesizing T-ZnOw and the optimum process conditions were explored. The structure and morphology of ZnO whiskers were characterized by Scanning Electron Microscopy （SEM） and X-ray diffraction（XRD）. The results show that these whiskers are single crystal with hexagonal wurtzite structure, length of whiskers range from 30μm to 65μm, the average length is 50μm, diameter of whiskers range from 2μm to 5μm, and the average diameter is 3μm. The growth of ZnO whiskers is determined mainly by two factors: one is the supersaturation of ZnO above the substrates, and the other is the crystallization property of ZnO material itself. The supersaturation of ZnO is the most impotant and can be regulated by controlling the temperature and reaction rate. The experimental results showed that when pre-heating rate is 5°C/min, the morphology of T-ZnOw is the most perfect and the yield is as high as 95 percent. With the improvement of pre-heating rate, the product is uneven tetrapods zinc oxide whiskers, and whisker size increases. With the reaction temperature increasing, whisker size reduced, but the yields and integrity of whisker have decreased.In this paper, intrinsic defects doping of the Tetra-ZnO whiskers were used to make a breakthrough in conducting electricity function. The micro-morphology, crystal structure, conducting properties of doped T-ZnOw were measured and analyzed. T-ZnOw were doped with Al、Ga by solution absorption blending pretreatment following by high temperature diffusing process. The result showed that T-ZnOw lost parts of needle point and some grains covered the whiskers surface. The formation of ZnGa₂O₄ and ZnAl₂O₄ can be observed by carefully examining the XRD patterns of doped T-ZnOw especially when dealing with highly doped samples. The electric conducting properties of the doped samples were characterized by electric resistance tests. Both Al and Ga doped T-ZnOw have an increase in conductivity. The electrical resistivity of T-ZnOw doped with Al reduces by four orders of magnitude, and for T-ZnOw doped with Ga, it decresed by seven orders of magnitude.

One of the most important used in modern coordination chemistry is the aspect of N-heteroaromatic ligands, which largely based on pyridine, 2,2′-bipyridine, melamine, and 2,2′:6′,2″-terpyridine （simply terpyridine）, have become an ever-expanding synthetic, application and structural frontier. Terpyridine ligands and the tailored terpyridine derivatives （especially 4′- functionalized terpyridines） are stronge tridentate ligands and have much advances and ever-expanding potential applications. Their well-known characteristics are applied in the fields of optical, catalytic, molecular recognition, gas storage, solar cell and so on. Also they could self-assemble lots of intriguing topological structures.Firstly, this thesis focuses on the synthesis of three 4′- functionalized terpyridine with 4-hydroxyphenyl、2-furyl and carboxylic acid. Several coordination compounds have been prepared by the reaction of d¹⁰ metals (Cd²⁺、Zn²⁺) with these ligands. All compounds are characterized by elemental analysis, IR, emission spectra and single-crystal X-ray diffraction.On the other hand, we think melamine and 2,6-bis（2-furyl）pyridine are very useful terpyridine-like ligands. Three novel melamine complexes with copper（II） including sandwich and extensive hydrogen bonds were obtained. Moreover, a new ligand of 4-（4′-Hydroxyphenyl）-2,6-bis（2-furyl）pyridine has been synthesized and may be uesd as pH sensor.In detail, the work is divided into six chapters as following:In Chapter 1, the research background of the synthesis of 4′-functionallized terpyridine and the current survey of terpyridine coordination compounds in particular optical properties and supermolecular assemblies are concisely introduced. A survey of melamine and 2,6-bis（2-furyl）pyridine are also mentioned.In Chapter 2, the cadmium（II） complex, Cd（p-HO-ptpy）Cl₂, p-HO-ptpy being a tridentate ligand 4′-（4-hydroxyphenyl）-2,2′:6′,2″-terpyridine has been synthesized and the crystal structure is determined using X-ray crystallography. Furthermore, its luminescent and electrochemical properties compared with the ligand have been investigated.In Chapter 3, the cadmium（II） complex, [Cd（ftpy）I₂]·CHCl₃, which ftpy being a ligand of 4′-（2-furyl）-2,2′:6′,2″-terpyridine has been synthesized. Furthermore, its crystal structure and luminescent properties compared with the ligand have been investigated.In Chapter 4, five mononuclear complexes c1-c5 and a mononuclear polymer c6 containing the ligand of 2,2′:6′,2″-terpyridine-4′-carboxylic acid （Hctpy） were prepared by hydrothermal method. The metallic ions in c1-c5 have distorted octahedral coordinations with six nitrogens from two molecules of Hctpy. But 1D chain structure of complex c6 is built by carboxylic acid of Hctpy and resulted in the enhanced emission band. The coordination mode of c6 has never been reported.In Chapter 5, a new ligand of 4-（4-Hydroxyphenyl）-2,6-bis（2-furyl）pyridine had been synthesized by two methods. Furthermore, this compound exhibits novel ultraviolet and electrochemical properties under the influence of pH value. The reason and the mechanism of Hpfpy may be tentatively assigned.In Chapter 6, three copper（II） coordination compounds have been synthesized and researched by cyclic voltammograms. Two novel melamine coordination compounds of them including the copper directly bonded to the aromatic rings of melamine have extensive hydrogen bonds and consolidate a 2-D sheets. Interestingly, one is a dinucear complex with a paddle wheel structure in which the apical positions are occupied specially by two different donor ligands.

The functional material research is one of the active field in chemistry and material.It is an essential way to synthisize some novel functional materials based on the characteristic of supramolecular compounds.In recent years,this has promoted the research into the synthesis and characterization of ionic organic supramolecular and coordination polymers.The series characteristic catalysts,nanometer materials,electric and magnetic materials had been synthesized.In this paper,we designed and synthisized a series of hydrogen bond assisted electrostatic supramolecular polymers and coordination polymers.Further, their optical and magnetic properties were studied.By the addition and oxidation reactions ofα-hydrogen-free nitriles with various amide lithium,ten novel compounds were prepared and characterized.The fluorescence and magnetic properties were determined. The detailed contents are divided into four sections:PartⅠ:A briefing on the latest theoretical and applied progress of supramolecular chemistry was given.Especially the development of the synthises and properties on ionic supramolecular polymers and coordination polymers.PartⅡ:The reaction of LiN（SiMe₃）₂ with 1,4-dicyanobenzene in the ratio of 1:1 or 1:2 were carried out,followed the metatheses of chlorodiphenylphosphine and oxidizing by hydrogen peroxide,two compounds,[C₆H₄（1,4-C（NH₂）（=NPPh₂））₂]L₁ and[4-CN-C₆H₄-C（NH₂）₂] [Ph₂PO₂]L₂ were prepared.With the similar reaction of dimethylamide lithium or diethylamide lithium with cyanobenzene,1,4-,1,3-, 1,2-dicyanobenzene or tolunitriles,total of five compounds,3,4,5,6 and 8,were prepared.The molecular structures of these compounds were determined by single crystal X-ray diffraction.The solid and solution fluorescence properties of compounds 3,6,8 were measured.PartⅢ:In the reactions of compounds L₁,L₂ with the transition metal and the main group metals salts,the anion of L₂ was replaced by chloride of copper chloride dihydrate or nitrate of hexahydrate zinc nitrate.Two novel supramolecular ionic polymers 9 and 10 were formed. Under hydrothermal conditions,the compound 11 was synthesized by L₁ and the cobalt chloride,it is an amorphous fibrous coordination polymer. According to the analysis results of compound 11,the ligand is diphenylphosphinate anion L₃.Then we used diphenylphosphinate sodium to replace L₁ and obtained the compound 11 too.It is noted that this is the first amorphous fibrous coordination polymer based on our knowledgement.Samely,the amorphous fibrous diphenylphosphinate zinc（Ⅱ） and lanthanum（Ⅲ） coordination polymer were synthesized.The magnetic measurement revealed that the magnetic property of amorphous fibrous diphenylphosphinate cobalt（Ⅱ） is as same as that of the crystalline.PartⅣ:The contents of Chapter 1-3 were summarized.The rule in the process of synthesis for diphenylphosphinate organic or metallic compounds was submitted.The application of these compounds in optical and the magnetic materials was viewed.

In recent years, there have been increasing research interests focused on tetrazolate complexes. This is mainly because tetrazole compounds, as polydentate N-donor ligands with diverse coordination modes, can build a variety of metal-organic coordination polymers. Recently, Sharpless et al. reported a simple, safe and environmentally friendly process for the preparation of 5-substituted 1H-tetrazoles, through the [2+3] cycloaddition reactions of nitriles with azide in the presence of zinc salt as Lewis acid in water. This dissertation mainly focuses on the in situ hydro(solvo)thermal syntheses, structures and luminescencent properties of series of tetrazolate-based coordination complexes. The thesis is divided into three chapters.In the first chapter, the research background is concisely introduced by highlighting recent advances of crystal engineering on metal-organic complexes, and illustrating the influencing factors in the designed syntheses and structures of metal-organic complexes, including temperature, pH value, solvents, anions and template agents. In addition, summary of research progresses on the syntheses, structures, properties and applications of tetrazolate complexes in the past few years, are presented. Finally, the aims and advances of this work are also outlined.The second chapter, focuses on the systematic investigation of the influencing factors such as temperature, pH value, solvents, anions and template agents on the hydro(solvo)thermal in situ generated tetrazolate coordination architectures. A series of new metal-organic complexes: [Cu(pzta)2 (H2O)2 ] (1), [Cu(pzta)2(NH3)2] (2), [Cu(pzta)2 ]n (3), [Cu(pzta)2 ]n (4), {[Cu2 (pzta)2 CN](DMF)} n (5), [Cu 3 (pzta)2 Br]n (6) [pzta = pyrazinyl tetrazolate] have been achieved by hydrothermal synthesis from pyrazinecarbonitrile and sodium azide or pyrazinyl tetrazolate ligand with different coppe salts. Complexes 1 and 2 contain similar Cu(pzta)2 mononuclear unit with the difference of the axial ligands. Complex 3 is a 1D chain polymer. Complex 4 and 5 formed the 2D sheet stuctures, respectively. Interestingly, the wave-shaped 2D architecture of complex 5 contains 1D channel. Complex 6 is a 3D structure constructed from copper-pyrazinyl-tetrazolate helices linked via CuBr chains. The dimensionalities of complexes 1-6 span from mononuclear (1, 2), one- (3), two- (4,5) to three- (6) dimensions, which indicates that the synthetic conditions play important roles in the framework formation of the in situ generated tetrazolate complexes. In chapter 3, six new coordination compounds containing carboxylate-tetrazolate ligands are obtained by solvo(hydro)thermal in situ reactions using dicyano reactants: [Ni(tacapy)(H 2 O) 2 ]2 (7), [Co(tacapy)(H2 O)3]2 (8), [Co(tacapy)(H2 O) 4 ]2 (9), [Mn(tacapy)(H2O) 4 ]n (10), [Cd(tacapy)]n (11) (tacapy = tetrazolate carboxylate pyridine), [Cd(tacapz)]n (12) (tacapz = tetrazolate carboxyl pyrazine). Complex 7-9 are zero-dimensional binuclear structures, which are extended into 3D supramolecular architectures via intermolecular hydrogen bonding in their crystal packings. Complex 7 and 8 can be simplified to a NaCl–like six-connected pcu hydrogen-bonding network, while complex 9 can be seen as a (6,10) connected hydrogen-bonding network with the symbol of (34 ?4 8 ?5 3)(38? 4 18 ?5 14 ?6 5). Complex 10 is a one-dimensional polymeric chain. Complex 11 and 12 are both three-dimensional polymers. Complex 11 can be simplified to a six-connected network with the symbol (36?66?73), and complex 12 is a four-connected network with the symbol 42 ?6 3?8. An interesting phenomenon occurs in the syntheses and structures of the six complexes, that in these reactions only one cyano group of the dicyano reactant undergoes cycloaddition to generate to tetrazolate group, while the other cyano group is always hydrolyzed into carboxlate group. Furthermore, complexes 11 and 12 exhibit strong photoluminescence.

The syntheses of complexes Ba[M（nta）Cl]·3H₂O (M = Cu²⁺, Co²⁺, Ni²⁺) and [M（H₂O）₆]_n[Cu₂（nta）₂]_n·2nH₂O (M=Co²⁺, Ni²⁺) were investigated in the system, the results show that: the substitution of two different transition-metal ions between the complexes of Ba[M（nta）Cl]·3H₂O(M=Cu²⁺, Co²⁺, Ni²⁺)and copper sulfate pentahydrate had reacted in the solution, and a new polymeric dinuclear copper（Ⅱ） nitrilotriacetate was synthesized. At the same time, the synthese ways and structure character were discussed in the paper respectively.

Cyclodextrins (CDs) has hydrophile exterior and hydrophobic central cavity, that results in its ability to form inclusion complexes with a variety of hydrophobic molecules with suitable shape and size in aqueous solution. The physicochemical properties of the included guest molecules are different from the pre-included compounds in terms of solubility, spectral and chromatographic properties, et al. Such beneficial property has made it among the most widely used host molecule of supramolecular chemistry and been applied in many fields, including synthesis chemistry, analytical chemistry, pharmaceuticals, and so on. Understanding of the supramolecular structure of its inclusion complexes is the basis of its research and application. X-ray crystallography is the most precise technique to explore the detail intermolecular interaction. Therefore, the study of cyclodextrins and their inclusion complexes can help us understand the weak molecular interactions deeply and reveal the nature of inclusion complexes.The crystals ofβ-CD-o-aminobenzoic acid,β-CD-p-aminobenzoic acid,β-CD-1,10-phenanthroline andβ-CD-adipic acid were successfully obtained and were analyzed by X-ray diffraction method at the same time. With the four crystal datas collected in this paper and crystal datas already reported, detailed analysis and comparison of the four crystal datas were carried out. Through studies we can find out that there are lots of hydrogen bonds formed betweenβ-CDs,β-CD and guest molecules andβ-CD and water molecules in the four crystal structures and these hydrogen bonds form a dense hydrogen-bond network. These hydrogen bonds are the main force to keep the ring conformation ofβ-CD molecules and the guest molecules in position. At the same tinme, we can get the following conclusion that the structure of the guest molecules along with the co-crystallized water molecules play an important role in the formation of the complex and the crystal packing.

As one kind of new advanced materials, Mg-based alloys with additions of rare earth elements have been paid to more attentions. Mg-based alloys own excellent properties, and the special structures of rare earth elements also play an important role in improving the intensity of magnesium based alloys. Many Mg-Zn-RE alloys have been widely used in many fields. However,up to now, the phase diagrams of the Mg-Zn-Ce system could not provide enough information to guide alloy design. Design of the new alloys and improvement on the properties of the existed alloys were restricted. So it is very important to study on the compounds and the related phases equilibria in the Mg-rich corner of the Mg-Zn-Ce system.By means of conventional equilibrated alloy methods, compositions and structure of the compounds and the related phase equilibria in the Mg-rich corner of the Mg-Zn-Ce system have been researched through the microstructure observation, electron probe microanalysis, X-ray diffraction and electron diffraction on the alloys of Mg81Zn17.5Ce1.5、Mg90Zn5Ce5、Mg88Zn2Ce10、Mg58Zn37Ce5、Mg93Ce5Zn2、Mg80Ce5Zn15、Mg92Ce7Zn1、Mg86Ce3.5Zn10.5 Mg87Zn8Ce5 treated at 350、300 and 200℃.It has been shown that no liquid exists, and only solid state phase equilibria exist in the Mg-rich corner of the Mg-Zn-Ce system below 350℃. At 350℃, the linear compound Mg92-xZnxCe8 (T phase) with 8at% Ce and continued changing of Zn content exists in the Mg-rich corner of the Mg-Zn-Ce system. The composition range of the T phase is Mg:48.8～73.4at%, Zn:2.3～43.6at%, Ce:7.64～7.86 at%. The T phase has a C-centred orthorhombic crystal structure. The broad two-phase region (Mg)+T and the three-phase region (Mg)+T+MgZn(Ce) exist in the Mg-rich corner of the Mg-Zn-Ce system at 350℃. The two-phase region (Mg)+Mg12Ce(Zn) also exists in the Mg-rich corner of the Mg-Zn-Ce system at 350℃.Also it has been shown that the linear compound T could exist stably at the temperature range of 350～200℃. The phase regions of (Mg)+Mg12Ce(Zn), (Mg)+T and (Mg)+ MgZn(Ce) +T also exist in the Mg-rich corner of the Mg-Zn-Ce system at 300℃and 200℃, and the shape of the three phase region is almost the same at 350～200℃.

Organic carboxylic acids possess the hard-base oxygen atoms that are affinitive toward rare earth metal ions and so are commonly used for synthesis of rare earth metal complexes. Pyrazine-2,3-dicarboxylic and pyridine-2,3-dicarboxylic acids, like benzen-1,2-dicarboxylic acid, have flexible coordination and so can be applied for construction of diverse structured and functionalised coordination polymers of rare earth metals. The dissertation, in the principles of molecule design and self-assembly of supramolecular chemistry and by hydrothermal reactions using azohetero aromatic bicarboxylic acids as main ligands, obtained a series of coordination polymers, which have been characterized by microanalysis, X-ray single crystal and powder diffractions, IR, and so on. Some of the polymers, showing fine photoluminescence have also been investigated in purpose of providing more evidences to the studies on such a kind of compounds.With coordination of 2,2′-bipyridine-3,3′-dicarboxylic acid as main ligand to La and Nd,two 2D coordination polymers, {[Ln2(bpdc)3(H2O)2]·4.5H2O}n ( Ln=La , Nd ) were synthesized. Furthermore, by adding different second ligands to these reactions, six more products with mix ligands ({[Nd2(bpdc)3(H2O)2]·2H2O·(bpy)}n、[Ln(bpdc)(Ho-phic)]n ( Ln=La , Nd )、{[Ln(bpdc)(Ho-phic)]·2H2O}n(Ln=Eu,Tb)、{[La(bpdc)(adi)0.5(H2O)2]·3 H2O }n) were isolated. Structures of these complexes reveal that rare earth metal ions are coordinated by oxygen of bpdc only, leaving nitrogen atoms free. This offers an evidence supportive to Lewis acid-base theory. More than that, from the isolated compounds, it is seen that the metal ions are all nine coordinated, except for 8. Under the given conditions, bpdc exhibits three coordination modes, two of which lead to one-dimensional (1D) chain and the remaining one leads to 2D network. If add phthalic acid as second ligand to reaction, owing to the closeness of two carboxylates which lead to chelation and hindrance, the polymers are usually 1D structured. Besides, we found also that coordination mode of ligand is influence by many other factors, for examples, presence of auxiliary ligand, nature of metal ion, and reaction conditions, such as temperature, stoichiometry, pH value, etc.. Pyrazine-2,3-dicarboxylic acid (pzdc), like 2,2′-bipyridine-3,3′-dicarboxylic acid, belongs to azo-containing aromatic ligand, but structurally it is more rigid. This part describe the use of pzdc as main ligand to obtain complexes of neodymium ({[Nd2(pzdc)3(H2O)]·2H2O}n and{[Nd2(pzdc)3(H2O)7]·1.5H2O}n). The effort revealed a diversity of polydentate coordination modes of pzdc and meanwhile found that coordination of pzdc with rare earth metal present higher coordination numbers and more complicated modes than coordination to transition metal ion. With increase of coordination number and complication of coordination mode of pzdc, the complexes show more complex structures. After that, we introduced flexible ligand, hexanoic acid-into the reactions, therewith obtaining a porous coordination polymer, {[La(pzdc)(adi)0.5(H2O)]·2H2O}n. It implicates that introduction of flexible aliphatic acid as second ligand into the reaction, when condition is suitable, can form structurally regular porous coordination frameworks.With consideration of the free coordination of nitrogen atoms of dicarboxylic acids in the synthesized rare earth metal complexes and selectivity of metal ions, we added transition metal ions, combined with rare earth metal, into the reactions and so were afforded four coordination polymers, [LnNi(bpdc)3(H2O)4]n(Ln=La,Nd)and {[Ln2Ni2(bpdc)5(H2O)7]·5H2O}n(Ln=La,Nd). These 3D metal-organic frameworks show an assembly from 1D and 2D structures. What is more, the endeavour obtained also two groups of complexes of 3d-4f with combination uses of rigid pydc with flexible butanoic and hexanoic acids. The resultant coordination polymers are highly porous, possessing the accessible voids up to 28.2 and 41.8% respectively. On basis of the observation, it is predictable that fabrication of MOF with various pore sizes is possible through adjusting the lengths of ligands.

In this thesis, we have reviewed the recent advances in the studies on thesynthesis, action mechanism and biological activities of triazoles and benzotriazoles,the active group of benzotriazole were inducted into the target compounds accordingto the concept of bioisosterism. twenty-five novel benzotriazole compounds in fourtypes of structure were designed and synthesized. They are summarized as follows:The structures of the novel benzotriazole compounds that were designed andsynthesized in four types were confirmed by means of 1HNMR, IR, EA and X-raysingle-crystal diffraction method determination. The antimicrobial activities weretested too. The contents and the primary contributions of the research are summarizedas follows:1. Twenty-five new compounds containing benzotriazole group were designedand synthesized. Their structures were confirmed with IR, MS, 1H NMR, EAand X-ray single-crystal diffraction method determination.2. Better synthesize method of desirable yield was studied. 3. Antimicrobial activities of new compounds were tested in MTT method andall the compounds were found to show some antimicrobial activities.

Seven lanthanide oxalate-oxydiacetate mixed ligand coordination polymers {[Ln（oda）（H₂O）_x]₂（ox）}_n [ x = 3 for Ln = La, Ce, Pr, Nd, Gd, Tb and x = 2 for Er ] have been synthesized by the reaction of oxydiacetic acid （H2oda） and corresponding lanthanide oxide, nitrate, chloride or carbonate in high purity and higher yield under mild hydrothermal conditions. The oxydiacetic acid was decomposed into oxalic acid in this reaction condition. The seven compounds have been characterized by EA, IR and X-ray diffraction analysis. They have similar composition with the difference in the number of water molecules, and all complexes crystallize in the monoclinic systems and space groups P21/c. In the crystal structures of all the seven compounds, the oxydiacetate ligands and the lanthanide atoms build a chain, and the oxalate groups bridge the two chains to form the double-chain ladder-shaped structures. The one-dimensional double-chains are connected by intermolecular hydrogen bonds to form the two-dimensional network structure. Approximately 3.0×6.4 （A|°）2 rhombus channels exist in the seven compounds {[Ln（oda）（H₂O）_x]₂（ox）}_n, so they can be used as gas-storage materials.The amide-type compound, N,N’-bis（p-methoxyphenyl）-3-oxapentanediamide （L）, was synthesized by oxydiacetic acid, and the reaction of lantanide nitrate with L produced nine complexes Ln（NO₃）₃·2L, of which two single crystals, Pr（NO₃）₃·2L and Nd（NO₃）₃·2L, suitable for X-ray crystallographic analysis were obtained. The X-ray crystal structures of the two compounds show that each ligand in compounds was tridentate coordination to form two stable planar five-membered chelate rings. One nitrate group coordinated bidentately with lanthanum atoms, and the other two groups were uncoordinated and balanced the charge. The hydrogen bonds in the compounds linked molecules to form a tri-dimensional network structure.