Syntheses, Structures And Properties Of Coordination Polymers Based On Different Flexible Pyridyl-amide And Various Organic Carboxylates Co-ligands

In this thesis, use four kinds of different flexible N1,N4-di(pyridin-3-yl)naphthalene-1,4-dicarboxamide(3-dpna), N1,N4-di(pyridin-4-yl)naphthalene-1,4-dicarboxamide(4-dpna/4-bpah), N,N′-bis(4-pyridinecarboxamide)-1,2-cyclohexane(4-bpcc), N,N′-bis(3-pyridinecarboxamide)-1,4-benzene(3-bpcb), N,N′-bis(4-pyridylformyl)piperazine(4-bpfp), N,N′-bis(3-pyridinecarboxamide)-1,2-cyclohexane(3-bpcc) and three aminopyridine derivatives with different length and coordination groups, [3,3’-azopyridine(3-azpy), N-(pyridin-3-yl)pyrazine-2-carboxamide(3-ppca),(E)-4,4’-(ethene-1,2-diyl)bis(N-pyridin-3-yl)benzamide(3-ebpba)] as main ligands, and use different aromatic dicarboxylic acids [1,3,5-benzenetricarboxylic acid(1,3,5-H3BTC), thiophene-2,5-dicarboxylic acid(2,5-H2tdca), 3,5-dinitrobenzoic acid(3,5-Hdnb), 5-nitroisophthalic acid(5-H2nip)and1,2-phenylenediacetic acid(H2pda)] as auxiliary ligands, and use Co(II)/Ni(II)/Cu(II)/Zn(II)/Cd(II) as metal ions under hydrothermal conditions. Nineteen new complexes have been abtained and characterized by single-crystal X-ray diffraction, IR, TG, and PXRD. The fluorescent property, electrochemical behavior, and photocatalytic activity of some polymers have been studied.1. Purposefully synthesized under hydrothermal conditions(3-dpna/4-dpna) as main ligands, and 1,3,5-H3BTC/H2 tdca for auxiliary ligands, eleven new complexes have been synthesized. The influences of metal(II) ions and N-donor ligands on the structures of the title compounds were investigated. [Co(3-dpna)(1,3,5-HBTC)]·2H2O(1) [Ni(3-dpna)1.5(1,3,5-HBTC)(H2O)2](2)[Cu(3-dpna)(1,3,5-HBTC)]·H2O(3) [Zn(3-dpna)(1,3,5-HBTC)]·2H2O(4) [Cd(3-dpna)(1,3,5-HBTC)(H2O)]·2H2O(5) [Co(4-dpna)-(1,3,5-HBTC)]·4H2O(6) [Ni(4-dpna)(1,3,5-BTC)2/3](7) [Cu(4-dpna)(1,3,5-BTC)2/3](8) [Zn(4-Hdpna)(1,3,5-BTC)](9) [Cd(4-dpna)(1,3,5-BTC)1/3Cl](10) [Cu2(4-dpna)2(2,5-tdca)2](11) Complexes 1 and 4 exhibit similar 1D belt-like chains constructed from 1D left- and right-hand [Co-(3-dpna)]n helical chains and [Co-(1,3,5-HBTC)]n linear chains. Complex 2 furnishes a 1D [Ni-(3-dpna)1.5]n “loop + line” chain with 1,3,5-HBTC anions hanging on both sides. Complex 3 features a 2D sql network based on [Cu-(3-dpna)]n meso-helical chains and [Cu-(1,3,5-HBTC)]n linear chains. Complex 5 shows a 1D ladder-like chain constructed from [Cd-1,3,5-HBTC]n linear chains and [Cd2(3-dpna)2] loops. Complex 6 displays a 2D double sheet containing(H2O)8 clusters. Complexes 7 and 8 possess similar 3D(3,4)-connected frameworks with the(63)2(64·8·10)3 topology containing a dodecagon-shape cavity and a hexagonal cavity, respectively. Complex 9 shows a 2D network, in which one pyridine nitrogen atom of 4-dpna was protonated. Complex 10 is a 3D(3,5)-connected framework with(3·44·63·82)3(63) topology. All the 1D chains and 2D networks are further extended into 2D supramolecular sheets or 3D supramolecular frameworks through hydrogen-bonding interactions.2. Five new Cu(II) coordination polymers(CPs) based on 3-bpcc/4-bpcc ligands and different nitro-substituted carboxylates(3,5-Hdnb and 5-H2nip), were synthesized under hydrothermal conditions. [Cu(3,5-dnb)(μ2-OH)](12) [Cu4(4-bpcc)2(3,5-dnb)6(μ3-OH)2(H2O)2](13) [Cu(4-bpcc)2(5-Hnip)2](14) [Cu3(4-bpcc)(5-nip)2(5-Hnip)(μ3-OH)(H2O)]·4H2O(15) [Cu(3-bpcc)(5-nip)]·2H2O(16)Complex 12 shows a 3D framework, which features a(3,5)-connected topology with the Schl?fli symbol of {3·72}{32·75·83}. Complex 13 displays a 3D supramolecular structure based on the tetranuclear [Cu4(3,5-dnb)6(μ3-OH)2] clusters, while complex 14 presents a 3D supramolecular architecture with mononuclear Cu(II) subunits. Complex 15 was obtained at a higher p H value than that in 14, which exhibits a uninodal 5-connected 3D bnn framework constructed from 1D ladder-like chains and μ2-bridging 4-bpcc ligands. Complex 16 is a 2D(4, 4)-network based on a 1D [Cu(3-bpcc)]n meso-helixe and a 1D [Cu(5-nip)]n zigzag chains. The bis-pyridyl-bis-amide ligands and nitro-substituted carboxylates, as well as p H show great influence on the formation and various structures of the title complexes.3. Three Cu(II) metal-organic frameworks(MOFs) based on 1,3,5-benzenetricarboxylic acid(H3BTC) and three aminopyridine derivatives with different length and coordination groups(3-azpy, 3-ppca, 3-ebpba) have been hydrothermally synthesized. [Cu2(3-azpy)(HBTC)(H2BTC)(μ3-OH)(H2O)2](17) [Cu2(3-ppca)(BTC)(H2O)3]·H2O(18) [Cu2(3-ebpba)(BTC)(μ3-OH)](19) Complex 17 exhibits a 2D layer, which has a 1D ladder-like chain with tetranuclear copper clusters. Complex 18 shows a rare 3D framework, which features a(3,3,3,3)-connected topology with the Schl?fli symbol of {8·10·12}2{82·10}2. Complex 19 exhibits a(3,8)-connected {4·62}2{42·622·7·83} topology based on tetranuclear copper clusters. The influence of aminopyridine-based ligands on the structures and properties of the title complexes has been discussed. The electrocatalytic and photocatalytic properties of complexes 17–19 have also been investigated in detail.4. Six new MOCPs based on 3-bpcb, 4-bpah, and 4-bpfp ligands and 1,2-H2 pda, were synthesized under hydrothermal conditions. [Cu(3-bpcb)(1,2-pda)]·2H2O(20) [Cd(3-bpcb)0.5(1,2-pda)(H2O)](21) [Cu(4-bpah)(1,2-pda)(H2O)]·H2O(22) [Ni2(4-bpah)2(1,2-pda)2(μ2-H2O)](23)[Cu3(4-bpfp)(1,2-pda)2(μ2-OH)2](24) [Co(4-bpfp)0.5(1,2-pda)(H2O)](25) Complexes 20–23 show four different 2D layer structures with(42·67·8)(42·6),(42·63.8)(42·6), {44·62}, and(8)(42·6)(42·67·8) topology, respectively. Complex 24 exhibits a long topological vertex Schl?fli symbol(3·4·5)2(32·42·52·614·74·83·9)(32·63·7). Complex 25 displays a 3D network with 3,4-connected(42·63·8)(42·6) topology. The diverse arrangements of the complexes show the remarkable sensitivity of the metal(II)-H2 pda system to the different bis-pyridyl-bis-amide ligands.