| In this thesis,[1,1':3',1''-terphenyl]-3,3'',5,5''-tetracarboxylic acid?H4L1?as one kind of tetracarboxylateacid,3,5-di?3'5'-dicarboxyphenyl?benzoicacid?H5L2?and2,4-di?3,5-dicarboxyphenyl?benzoic acid?H5L3?as two kinds of pentacarboxylate acid ligands have been used to synthesize four new coordination complexes based on Zn? or Cd? ions.3,4-di?3,5-dicarboxyphenyl?phthalic acid?H6L4?as hexacarboxylate acid ligands have been used to react with Zn?,Cd?,Cu?,Mn? ions to obtain four new coordination complexes.H6L4 as the main ligand,bis-pyridyl ligands as the auxiliary ligands have been used to react with Mn?,Co?,Ni? ions to obtain five new coordination complexes.The thirteen new complexes have been characterized in detailed by single-crystal X-ray diffraction,elemental analyses,infrared spectroscopy?IR?and X-ray powder diffraction?XRPD?.In addition,thermogravimetric analysis?TGA?,fluorescence spectroscopy,electrochemical behaviors and photocatalytic properties have been studied systematically.1.Four new coordination complexes based on Zn? or Cd? ions have been synthesized in the solvothermal conditions using[1,1':3',1''-terphenyl]-3,3'',5,5''-tetracarboxylic acid?H4L1?as tetracarboxylate acid,3,5-di?3'5'-dicarboxyphenyl?benzoic acid?H5L2?and2,4-di?3,5-dicarboxyphenyl?benzoic acid?H5L3?as three kinds of pentacarboxylate acid ligands.In addition,the effects of different metal ions and the different coordination modes of ligands on the structures of complexes have been studied.[Zn2?L1??H2O?2]n?1?[Zn2?HL2??H2O?]n?2?[Cd2?HL2??DMF?2]n?3?[Zn4?HL3?2?H2O?]n?4?Complex 1 features a?3,4,7?-connected{43·613·85}{43·63}{43}3D topology framework,which contains 1D chains formed by carboxyl oxygen atoms linking dual-core Zn? units.In the structure of complex 1,L1 ligand adopts double coordination and double chelate coordination mode.Complex 2 represents a?5,5?-connected{45·65}3D framework,containing 1D chains formed by ligands and dual-core Zn? units.HL2 ligand adopts double coordination and double chelate coordination mode.Complex 3 displays a?5,5?-connected{47·63}3D framework,containing 1D wave type chains formed by ligands and dual-core Cd? units.HL2 ligand adopts monodentate coordination,double coordination and double chelate coordination mode.Complex 4 features a?5,5,5,5?-connected{44·66}{46·64}3D complicated framework,including 1D chains formed by ligands and two kinds of dual-core Zn? units.HL3 ligand adopts monodentate coordination,double coordination and double chelate coordination mode.Moreover,the fluorescence intensities of complexes 1–4 in organic solvent containing nitrate,chloride and acetate were measured,and the performances of fluorescent recognition on Fe3+for complexes 1–4 were studied.2.Four new coordination complexes based on Zn?,Cd?,Cu?,Mn? ions have been synthesized in the solvothermal conditions and hydrothermal conditions using3,4-di?3,5-dicarboxyphenyl?phthalic acid?H6L4?ligand.In addition,the influences of different metal ions on the structures of complexes have been studied.{[Zn3?HL4?2]·[?CH3?2NH2]4}n?5?{[Cd3?L4?2]·[?CH3?2NH2]6}n?6?{[Cu5?HL4?2?H2O?12]·10H2O}n?7?{[Mn5?HL4?2?H2O?10]·3.5H2O}n?8?Complex 5 displays a?4,4,6?-connected{42·64}2{44·611}2{44·62}3D topology framework,which contains 1D chains formed by symmetric units with Zn? centered.In the structure of complex 5,HL4 ligand adopts monodentate coordination and double chelate coordination mode.Similar to complex 5,complex 6 represents a?4,4,6?-connected{42·64}2{44·611}2{44·62}3D topology framework,containing 1D chains formed by symmetric units with Cd? centered.L4 ligand adopts monodentate coordination and double chelate coordination mode.Complex 7 features a?3,4,3,4?-connected{42·6·123}{42·6}3D complicated framework,containing 1D chains formed by ligands and Cu? ions.HL4 ligand adopts monodentate coordination,double coordination,double chelate coordination and single bridged coordination mode.Complex 8 displays a?4,3,4,3,3,9,9?-connected{414·615·87}2{42·64}{43}2{45·6}2 3D complicated framework,including 1D chains formed by ligands and Mn? ions.HL4 ligand adopts monodentate coordination,single bridged coordination,double coordination and double chelate coordination mode.Moreover,the fluorescence intensities of complexes 5–6 in organic solvent containing nitrate,chloride and acetate were measured,and the performances of fluorescent recognition on Fe3+for complexes 5–6 were studied.In addition,when H2O2 existed,the photocatalytic properties of the degradation of methylene blue?MB?of complex 8 were studied.3.Five new coordination complexes based on Mn?,Co?,Ni? ions have been synthesized in the hydrothermal conditions using 3,4-di?3,5-dicarboxyphenyl?phthalic acid H6L4 as the main ligand,the rigid 4,4'-dipyridyl?bpy?and the weaker rigid1,2-bis?4-pyridyl?ethylene?bpe?as the auxiliary ligands.Moreover,the effects of different metal ions and the different coordination modes of auxiliary ligand on the structures of complexes have been studied.{[Mn2?H4L4?2?bpy?2?H2O?6]·?bpy?·4H2O}n?9?[Co3?L4??bpy?4?H2O?4]n?10?{[Co2.5?H3L4?2?bpe??Hbpe??H2O?5]·H2O}n?11?{[Ni?H4L4??bpy??H2O?4]·2H2O}n?12?{[Ni3?H3L4?2?bpe?3?H2O?4]·6H2O}n?13?Complex 9 represents a 1D chains formed by carboxyl oxygen atoms linking dual-core Mn? units.In the structure of complex 9,H4L4 ligand only adopts monodentate coordinationmode.Complex10displaysa?3,3,4,4,6?-connected{52·62·7·8}{52·6}2{54·66·72·83}3D framework,containing 1D chains formed by carboxyl oxygen atoms linking Co? ions with rhombus type.L4 ligand adopts monodentate coordination and double chelate coordination mode,and bpy ligand displays single coordination and double coordination mode.Complex 11 features a?4,4,3?-connected{4·82}2{42·82·102}{8·104·12}3D framework,containing 1D“?”type chains formed by carboxyl oxygen atoms linking Co? ions.H3L4 ligand adopts double bridged coordination and single coordination,and bpe ligand displays double coordination mode.Complex 12contains two kinds of chains,H4L4 ligand and bpe ligand linking Ni? ions,displaying a4-connected{65·8}3D framework.H4L4 ligand and bpy ligand adopt monodentate coordination,double coordination mode,respectively.Complex 13 features a?3,4?-connected{6·84·10}{62·8}2 3D supermolecule framework,containing two kinds of chains formed by bpe ligand linking Ni? ions.H3L4 ligand adopts double bridged coordination and monodentate coordination mode.In addition,when H2O2 existed,the photocatalytic properties for the degradation of methylene blue?MB?and Rhodamine B?RhB?of complex 9–13 were studied. |
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