Studies On Molecular Assembly And The Fluorescent Spectrometry Including Nitrogen And Oxygen Building Block

In this thesis, a series of building blocks have been obtained that have different figure including chain, V shape and triangle; and -diketone( 2,5-dihydroxycyclohexa- l,4-diene-l,4-dicarboxylate) derivatives are synthesized. We utilize the known structural compounds including N and O to coordinate to metallic ion. Moreover, the crystals of a series of compounds/complexes are obtained. The crystal structures of the compounds/complexes are determined by X-ray single crystal diffraction. The information of crystal structures from X-ray single crystal diffraction are utilized to search for the relationship between structure and function. My work is summarized as follows:1. The synthesis of Building blocks including N: (1)four lined ligands (L1,L₂,L3,L4) are synthesized by utilizing the Witting reaction; (2) two lined, a 'V shape' and a triangle ligands have been obtained by utilizing the Ullmann reaction; (3) two lined and a triangle shape ligands have been obtained by utilizing the condensation reaction.Their structures were confirmed with IR, 1H NMR and EA. And the crystal structures of eight building blocks and four intermediates are determined by X-ray single crystal diffraction. The crystal structures are studied at micro structure. And the environment of atomic arrangement and molecular accumulation were analysed through Mercury and Diamond software. At the same time, Optical physical properties of them were mensurated and analyzed.2. Three series of thirty-two p-diketone derivatives are synthesized. Their structures were confirmed with IR and 1H NMR. And the crystal structures of eight building blocks and four intermediates are determined by X-ray single crystal diffraction. The crystal structures are studied at micro structure. And the environment of atomic arrangement and molecular accumulation were analyzed through Mercury and Diamond softwares. At the same time, Optical physical properties of them were mensurated and analyzed.The synthesis method of 2,5-dihydroxycyclohexa- l,4-diene-l,4-dicarboxylate are studied. Through comparison, we conclude a synthetic route of easier disposal, higher yield and milder reaction by utilizing different solvent, catalyzer and temperature of the reaction.3. By self-assembly, five layer coordination complexes are synthesized [Cu(dippy)(ace)₂,(H₂dippy)(p-CH₃O-bic)₂,[Pb(dipic)]_n,Cu(dipic)(H₂O)₂]_n,[Cu(pic)₂(H₂O)₄]] and the other three complexes [Cu(H₂difpy)Cl₄,Ni(difpy) (ditbu)₂,{[(CH₃)₂NH₂]₃(Cd₃Cl₉)}∞]。The eight crystal structures are studied at microstructure. And the environment of atomic arrangement and molecular accumulation were analyzed through Mercury and Diamond software5. Cu(dippy)(ace)₂ forms a 'stairway' structure. Cu(H₂difpy)Cl₄ forms a 'reclining chair' structure; The parallel 'reclining chair' structures are connected. Ni(difpy)(ditbu)2 forms a 'W structure. The parallel 'W structures are connected. (H2dippy)(p-CH3O-bic)2, two supermolecules form a 'V structure and the limitless 'M or Z' chain is connected through 'V' structure. [Pb(dipic)]n exhibits a novel 2D framework which contains three-type of helical chains with the highest-stranded number of three in the entangled system and the reticular 2D framework through oxo-bridges forms a 3D layer structure. [Cu(dipic)(H₂O)₂]_n exhibits a novel 2D framework which contains single-helix chains in the entangled system through oxo-bridges. [Cu(pic)₂(H₂O)₄] exhibits a novel 2D framework which contains double-helix in the entangled system. {[(CH₃)₂NH₂]₃(Cd₃Cl₉)}∞exhibits a ID frame- work containing metal string complexes and quantum chemical calculations were performed with GAUSSIAN 03 program.4. Twenty-seven supermolecular complexes have been obtained by self- assembly utilizing the compounds (L₁,L₃ and L₁₁) with organic or inorganic acid. Optical physical properties of them were mensurated and analyzed. The fluorescence property of ligand L1 is influenced by 4-methoxybenzoic acid that is studied.5. One hundred and thirteen complexes have been obtained by utilizing the ligands( L1,L₂,L6,L7,L8,L9 and L10) and seventy-two complexes have been synthesized by utilizing the ligands including 0 to coordinate to metallic ion. Optical physical properties of them were mensurated and analyzed, respectively. Through comparison, we have searched for the relationship between structure and function.6. From thermodynamics, quantum chemical calculations were performed with GAUSSIAN 03 program. We determine the below reaction possible at room condition. Therefore, we conclude a kind of reaction feasible.