Synthesis, Structures, And Topologies Of Coordiuation Polymers Based On Tri(4-imidaolyphenyl)Amine Ligand

The aim of this thesis is the study of new coordination compounds based on tridentate tri(4-imidaolyphenyl)amine ligand and transition metal ions. The study on synthetic conditions and rules for these new compounds, topological analyses, and the exploration of relationships between structures and properties for these new compounds are also carried out.Nineteen new coordination compounds have been synthesized on the basis of hydrothermal technique and structurally characterized by elemental analyses, IR, XRPD, TG and single crystal X-ray diffractions. The thermal stabilities properties and fluorescent properties of some compounds have been studied.1. Four compounds based on tri(4-imidaolyphenyl)amine and different carboxylates have been synthesized. Compound 1 shows a 2D wave layer with (3,5)-connected (42·6)(42·67·8) topololgy. Compound 2 is a 2D→3D network with 44 topological layers. Compound 3 exhibits 3D framework with (3,4)-connected (5·62·82·9)(63·72·9)(73)(62·8) topology. Compound 4 is a 3D framework with (3,4,6)-connected (42·62·7·8)(4·6·83·10)(6·8·10)(44·52·67·7·8)(42·82·102) topology. [Mn(Tipa)(m-bdc)]·H2O (1) [Zn(Tipa)(m-bdc)]·H2O (2) [Zn2(Tipa)(btc)(μ2-O)]·2H2O (3) [Zn2(Tipa)(btca)]·3.5H2O (4)2. Four entangled coordination polymers based on tri(4-imidaolyphenyl)amine ligand and different carboxylates have been synthesized under hydrothermal condition. Compound 5 shows a 2-fold interpenetrated 3D framework with (3,5)-connected (63)(65·85) topology. Compound 6 is a 4-fold interpenetrated 3D framework with (10,3)-a topology. Compound 7 exhibits (3,4)-connected (4·82)(4·85) topological 3D network, where four independent networks interpenetrate each other to form a 4-fold interpenetation. Compound 8 is a fascinating 54-fold interpentration with (10,3)-a topology. [Cd(Tipa)(NH2-bdc)]·CH3OH·H2O (5) Cd(Tipa)(badc)(H2O) (6) [Ni2(Tipa)2(p-bdc)(H2O)2]2·Cl4·4H2O (7) [Ag3(OH)(H2O)2(Tipa)2.5][Mo2O7]·4.5H2O (8)3. Six new entangled polythreaded networks based on tri(4-imidaolyphenyl)amine ligand, different anions and transition metal ions have been synthesizd. Compounds 9 and 10 are 2D→2D polyrotaxane networks, where the free carboxylate anions sandwiching between polyrotaxane layers. Compounds 11 and 12 show the 2D→3D polyrotaxane frameworks. Compound 13 is a special polyrotaxane framework with both 2D→2D and 2D→3D features. Compound 14 is the first example of 2D→3D polyrotaxane in parallel fashion. [Ni2(Tipa)2(p-bdc)(H2O)4]·(p-bdc)·0.5H2O (9) [Cu2(Tipa)2(p-bdc)(CH3OH)(H2O)]·(p-bdc)·1.5(CH3OH)·4.5(H2O) (10) [Cd(Tipa)(NH2-bdc)2]·H2O (11) [Mn(Tipa)(NH2-bdc)2]·H2O (12) [Ni2(Tipa)2(p-bdc)2(H2O)2]·2.25H2O (13) [Cd(Tipa)Cl2]·H2O (14)4. Two interesting self-penetrating networks based on p-bdc anion, tri(4-imidaolyphenyl)amine ligand and metals have been synthesized under the hydrothermal condition. Compound 15 is a 3D self-penetrating framework with polyrotaxane feature, where two 3D frameworks interpenetrate each other to form a 2-fold interpentration. Compound 16 is a 3D self-penetrating framework with (4·62)(42·54·62·75·72·92)(52·66·75·82) topology, where two 3D frameworks interpenetrate each other to form a 2-fold interpentration. [Cd3(Tipa)2(p-bdc)2Cl2]·4H2O (15) [Co3(Tipa)2(p-bdc)3] (16)5. Three compounds based on 1,2,3-bta anion, tri(4-imidaolyphenyl)amine ligand and different metals have been synthesized under hydrothermal condition. For compound 17, tri(4-imidaolyphenyl)amine ligands connected pentanuclear ZnⅡclusters and ZnⅡ-O chains to form an infinite 3D framework. Compound 18 is a 3D framework with (3,6)-connected (63)(44·6n) topology based on trinuclear CdⅡcluster. Compound 19 is a novel 3D framework based on dodecanuclear CdⅡcluster with (3,6)-connected (63)(44·611) topology. [Zn7.5(Tipa)(1,2,3-bta)4(OH)3]·4H2O (17) [Cd3(Tipa)2(1,2,3-bta)2]·2.5H2O (18) [(Cd6(Tipa)2(1,2,3-bta)3(H2O)3]·3H2O (19)...