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Transition Metal Superamolecular Coordinate Polymer Construction and Structural Research

Author: WangJuanGang
Tutor: TangNing
School: Lanzhou University
Course: Inorganic Chemistry
Keywords: Metal organic framework crystal project intermolecular weak interaction crystal structure porous coordinate polymer spiral preparation coordinate polymer chain Chiral resolution
CLC: O641.4
Type: PhD thesis
Year: 2008
Downloads: 638
Quote: 3
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Abstract


In recent years, the most important subjects of intensively current research in coordination chemistry, supramolecular chemistry and crystal engineering have focused on building novel metal-organic supramolecular compounds through metal-ligand coordination and intermolecular interactions (hydrogen bonds, p-p stacking, etc.) between ligands. Design and synthesis of polynuclear, 3d-4f heterometallic and helical metal-organic supramolecular complexes with novel topological structures or special properties are of great interest at present, due to their ability to impart nonlinear optical, electro-chemicals, magnetics, catalysts, molecular devices, highly selective and specific molecular transformations, transport, and storage and polymorphism.This thesis covers following senven parts:1) In this part the concepts of coordination chemistry, metal organic supramolecular, metal-organic frameworks (MOFs), polymorphism and crystal engineering were simply introduced. The structural research approaches, single crystal growth technology, along with the significance and application of the study, were also discussed.2) With the rigid ligand 8- amino naphthoic acid, 4,4 ’ - the dipyridyl and the cobaltous chloride responded in the water - methyl alcohol’s component solvent that synthesizes coordinate polymer [Co(bipy)3(AM)(H2O)2. (AM)]n, with the ultimate analysis, the infrared spectrum carries on the attribute, has determined the preparation crystal structure with the X- ray unit crystal diffraction. Discovered through the crystal analysis: Coordinate polymer [Co(bipy)3(AM)(H2O)2. (AM)]n is univariate has the porous scalariform structure, the hole size for 8.498x8.528 A. 3) With the ligand 2,6- diphenic acids which and the zinc chloride easy to twist in the water - methyl alcohol component solvent responded that synthesizes coordinate polymer [Zn(dpa)H2O]n, with the ultimate analysis, the infrared spectrum carries on the attribute, has determined the preparation crystal structure with the X- ray crystal diffraction. Discovered through the crystal analysis: Coordinate polymer [Zn(dpa)H2O]n is double helix structure, between the Zn...Zn distance is 3.763, the spiralization cycle approximately is 5.960 A.4) 3,5- two carboxyl group Mi Zuo and the cupric chloride, the even hemimellitic acid (L1), 5- nitryl benzene dicarboxylic acid (L2) and the nickelous nitrate responded separately in the water - methyl alcohol’s component solvent that synthesizes coordinate polymer [Cu(Bzon)(H2O)2]n and[Ni3(L1)(L2)(H2O)12]n. With the ultimate analysis, the infrared spectrum carries on the attribute, has determined the preparation crystal structure with the X- ray crystal diffraction. Discovered through the crystal analysis: Preparation [Cu(Bzon)(H2O)2]n is the bimetal univariate chain structure; Preparation [Ni3(L1)(L2)(H2O)12]n was the Z univariate chain structure, on between the ligand 5- nitro-iaophthalic acid nitryl oxygen and the coordinate water has formed the intermolecular hydrogen bond, encircled the rule lozenge hole through such hydrogen bond connection chain and the chain.5 ) The L- tartaric acid and the ferrous sulfate - the link hexamethylene-diamine responded take (1R,2R) as the template in the water - methyl alcohol’s component solvent that synthesis chiral coordinate polymer [Fe2(L-Taric)2(H2O)]n and has determined its crystal structure. Discovered through the crystal analysis: Coordinate polymer [Fe2(L-Taric)2(H2O)]n is the space network structure. 6)The synthesis binuclear complexs[Co2(L3)2(C2H5OH)2Cl2], [Ni2(L3) 2(C2H5OH)4]as well as single nucleus complex[Gd(DHBA)3 (H2O) 4]and determines their crystal structure (between L=5- methyl 2- hydroxyl benzene two wo), through crystal analysis discovery biuclear complex [Co2 (L3) 2(C2H5OH)2Cl2]depends upon between C1...H-O the dual hydrogen bonds to connect the univariate chaining ultra molecular structure, between the ultra molecular chain has the obvious staggered p-p stack. Not only binuclear complex [Ni2 (L3) 2(C2H5OH)4]depends upon the O-H...O-NO2 hydrogen bond to connect the univariate chaining ultra molecular structure, between the preparation structural unit dependence ligand hydroxyl the hydrogen bond (O-H...O-H) connects assembles the univariate ultra molecular chain similarly, between the molecular chain has the obvious regular order p-p the stack. Reported a novel and efficient catalyst of dinuclear complex [Co2 (L3)2(C2H5OH)2Cl2] in conjunction with phenyltrimethylammonium tribromide (PTAT) for the coupling reaction of carbone dioxide and epoxides. and we discovered that binuclear complex[Co2 (L3) 2(C2H5OH)2Cl2]has the obvious catalytic activity under the promoter PTAT existence to the epoxide and the carbon dioxide, but binuclear complex [Ni2 (L3)2(C2H5OH)4] catalytic activity7) Using the chiral tartaric acid resolution racemization hexamethylene-diamine is the object of study, under the condition raises their unit crystal in the more or less the same, attempts to explain he solubility difference from their crystal structure difference in the solution .

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CLC: > Mathematical sciences and chemical > Chemistry > Physical Chemistry ( theoretical chemistry ),chemical physics > Structural Chemistry > Complex chemistry ( coordination chemistry )
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