Syntheses,Structures And Properties Of Coordination Polymers Based On Different Shapes Of Bis-pyridyl-bis-amides And Various Polycarboxylates Mixed-ligands

In this thesis, two semi-rigid bis-pyridyl-bis-amide ligands with different shapes N,N’-bis（pyridin-3-yl）-5-hydroxybenzene-1,3-dicarboxamide （3-bpha） and N,N’-bis（pyridine-4-yl）-1,4-benzenedicarboxamide （4-bmpbd） were selected as the main ligands and multiple polycarboxylates with different substitute groups, as well as the carboxyl position and number [1,3-benzenedicarboxylic acid （1,3-H₂BDC）,5-methylisophthalic acid （H₂MIP）,5-hydroxyisophthalic acid （H₂HIP）,1,3,5-benzenetricarboxylic acid （1,3,5-H3BTC）,5-nitroisophthalic acid （H₂NIP）,2,3-pyridinedicarboxylic acid （2,3-H₂PDC）,3-nitrophthalic acid （3-H₂NPH）,4-hydroxybenzoic acid （4-HHBC）,2,2’-biphenyldicarboxylic acid （2,2’-H₂BDC）,4,4’-oxybis(benzoic acid （H₂OBA）,2,5-（s-acetic acid）dimercapto-1,3,4-thiadiazole （H₂ADTZ） and 1,3-adamantanedicarboxylic acid （1,3-H₂ATDC）] as the auxiliary ligands to react with ZnⅡ/CdⅡ/CoⅡ atoms under hydrothermal/solvothermal conditions. Twenty-two new coordination polymers （CPs） have been synthesized and characterized by single-crystal X-ray diffraction, IR, PXRD and TG. The electrochemical properties, fluorescent properties and photocatalytic activities of some complexes have been investigated.1. A "V"-like semi-rigid bis-pyridyl-bis-amide ligand 3-bpha was used as the main ligand and various polycarboxylates as auxiliary ligands, thirteen complexes from OD to 3D have been hydrothermally synthesized and structurally characterized. Moreover, the influence of the transition metal ions and polycarboxylates on the final structures of CPs have been discussed in detail.[Cd（3-bpha）（1,3-BDC）（H₂O）]·3H₂O （1）[Cd（3-bpha）（MIP）（H₂O）]·H₂O （2）[Cd（3-bpha）（1,3,5-HBTC）（H₂O）]·3H₂O （3）[Cd（3-bpha）（HIP）]·3H₂O （4）[Zn（3-bpha）（HIP）]·3H₂O （5）[Zn（3-bpha）（MIP）] （6）[Zn（3-bpha）（NIP）] （7）[Co（3-bpha）₂（2,3-HPDC）₂] （8）[Co（3-bpha）（3-NPH）（H₂O）₂]·2H₂O （9）[Co（3-bpha）（1,3-BDC）]·4H₂O （10）[Co（3-bpha）（HIP）]·3H₂O （11）[Co（3-bpha）（MIP）（H₂O）]·H₂O （12）[Co3（3-bpha）₂（1,3,5-BTC）₂（H₂O）₄]·2H₂O （13）Complexes 1,2,3 and 5 are similar 1D channel-like structures. Complexes 4,10 and 11 are similar （2,3,5）-connected 2D networks with （42·6）（43·6·84·102）（4） topology. Complexes 6,7 and 12 are isostructural 2D 4-connected networks. Complex 8 is a discret 0D structure in which the 3-bpha ligands and the 2,3-HPDC anions act as the terminal groups simultaneously to coordinate with the CoⅡ ions. Complex 9 is a ID meso-helical chain. Complex 13 shows a 3D framework with （3,3,4）-connected （83）₄（84·102） topology. Different center metal ions and polycarboxylates play great effects on the structures of target complexes. Furthermore, the electrochemical properties of complexes 8-13, the fluorescent properties and the photocatalytic activities of 1-13 have been studied.2. Using the linear semi-rigid bis-pyridyl-bis-amide ligand 4-bmpbd and different polycarboxylates as the mixed ligands to react with CdⅡ ions under hydrothermal/solvothermal conditions. Nine new CPs from 1D to 3D have been presented and structurally characterized.[Cd3（4-bmbpd）₄Cl6（H₂O）₂] （14）[Cd（4-bmbpd）（2,2’-BDC）（H₂O）] （15）[Cd（4-bmbpd）（OBA）]·H₂O （16）[Cd（4-bmbpd）_0.5（ADTZ）（H₂0）]·H₂O（17）[Cd4（4-bmbpd）（1,3-ATDC）₄（H₂O）6]·2H₂O （18）[Cd（4-bmbpd）（3-NPH）（H₂O）]·H₂O （19）[Cd（4-bmbpd）_0.5（NIP）（H₂O）] （20）[Cd（4-bmbpd）_0.5（HIP）]·H₂O （21）[Cd3（4-bmbpd）₂（1,3,5-BTC）（H₂O）₄]·4H₂O （22）Single crystal X-ray analyses reveal that complex 14 shows a 1D wave-like double chain constructed from [Cd3（4-bmbpd）₂Cl6（H₂O）₂] subunits and μ2-bridging 4-bmbpd ligands. Complex 15 displays a 2D 4-connected layer structure consisted of 1D [Cd-4-bmbpd]n zigzag chains and 1D [Cd-2,2’-BDC]n single-strand helix chains. Complex 16 is also a 2D 4-connected network constituted of 1D [Cd-OBA]n linear chains and [Cd（4-bmbpd）]n wave-like chains. Complex 17 holds a （2,4,4）-connected 2D architecture based on [Cd2（ADTZ）₂] rings and μ4-bridging 4-bmbpd ligands with {42·82·102}{42·84}2{4}2 topology. Complex 18 exhibits an intriguing 1D chain constructed from [Cd4（1,3-ATDC）₄] rings and μ2/μ4-bridging 4-bmbpd ligands. Complex 19 presents a 1D ladder-shaped chain. Complex 20 is composed of a 3D （4,4）-connected framework giving an interesting self-penetrating architecture. Complex 21 is a 3D （4,5）-connected architecture with {44·62}{44·66} topology. Complex 22 shows a 3D （2,3,4,4）-connected framework, which contains [Cd-1,3,5-BTC]n 1D double chains. The versatile structures reveal the impact of the substitute groups as well as the carboxyl position and number of carboxyl group on the architectures. Furthermore, the effect of organic solvents on the fluorescent behaviors of 14-17 and 20-22, and the photocatalytic properties of 13-22 under UV irradiation have been investigated in detail.