Syntheses, Structures And Properties Of Coordination Polymers Based On Flexible/Semi-rigid Bis-pyridyl-bis-amide Ligands

In this thesis, four kinds of flexible N,N’-bis(3-pyridinecarboxamide)-1,2-ethane(3-dpye), N,N’-bis(3-pyridinecarboxamide)-1,3-propane (3-dpyp),N,N’-bis(3-pyridinecarboxamide)-1,4-butane (3-dpyb) orN,N’-bis(3-pyridinecarboxamide)-1,6-hexane (3-dpyh), two semi-rigidbis-pyridyl-bis-amide ligands N,N’-bis(3-pyridinecarboxamide)-1,2-cyclohexane(3-bpah) and N,N’-bis(4-pyridinecarboxamide)-1,2-cyclohexane (4-bpah) have beenselected as the main ligands and different aromatic dicarboxylic acids[1,2-benzenedicarboxylate (1,2-H2BDC),1,3-benzenedicarboxylate (1,3-H2BDC),1,4-benzenedicarboxylate (1,4-H2BDC),1,4-naphthalenedicarboxylic acid (1,4-H2NDC),3-nitrophthalic acid (3-H2NIP),5-nitroisophthalic acid (5-H2NIP),5-aminoisophthalicacid (5-H2AIP),5-sulfoisophthalic acid (5-H2SIP),5-methylisophthalic acid (5-H2MIP)]have been used as the auxiliary ligands to react with different transition metal ionsunder hydrothermal conditions. Forty six new complexes have been synthesized andcharacterized by elemental analyses, IR, PXRD, and single-crystal X-ray diffraction.The TG, electrochemical behavior, fluorescent property, and photocatalytic property ofsome polymers have been studied.1. Using the mixed ligands of the flexible bis-pyridyl-bis-amide ligands3-dpye,3-dpyp,3-dpyb or3-dpyh and different aromatic dicarboxylic acids, twenty-threeCu(II), Ni(II) or Co(II) coordination polymers from one-dimensional (1D) to threedimensional (3D) structures have been hydrothermally synthesized and structurallycharacterized. We study the influence of the flexible3-dpye,3-dpyp,3-dpyb or3-dpyh ligands and organic carboxylate auxiliary ligands on the sructures of complexes.[Cu(3-dpye)(1,3-BDC)]·3H2O (1)[Cu(3-dpye)(1,3-BDC)(H2O)]·H2O (2)[Cu(3-dpye)0.5(5-AIP)(H2O)](3)[Cu3(3-dpye)(1,2-BDC)2(μ2-OH)2](4)[Cu(3-dpye)(3-NIP)(H2O)]·3H2O (5)[Cu2(3-dpyp)(1,3-BDC)2(H2O)4]·3H2O (6)[Ni(3-dpyp)(1,3-BDC)(H2O)]·H2O (7)[Cu3(3-dpyb)(1,2-BDC)2(μ2-OH)2](8)[Cu3(3-dpyb)3(SIP)2(H2O)8]·6H2O (9)[Co(3-dpyb)(1,3-BDC)]·H2O (10)[Ni(3-dpyb)(1,3-BDC)(H2O)2]·H2O (11)[Cu(3-dpyh)0.5(1,2-BDC)]·H2O (12)[Cu(3-dpyh)0.5(1,4-BDC)(H2O)](13)[Cu(3-dpyh)0.5(5-AIP)(H2O)](14)[Cu(3-dpyh)(1,4-NDC)(H2O)]·3H2O (15)[Cu(3-dpyh)0.5(1,4-NDC)]·H2O (16)[Cu(3-dpyh)(3-NIP)(H2O)2](17)[Ni(3-dpyh)(3-NIP)(H2O)2](18)[Co(3-dpyh)(3-NIP)(H2O)2](19)[Co(3-dpyh)(5-NIP)]·H2O (20)[Co(3-dpyh)(5-MIP)]·H2O (21)[Co(3-dpyh)0.5(5-AIP)(H2O)]·2H2O (22)[Co(3-dpyh)(1,4-BDC)(H2O)2](23)The twenty-three complexes display versatile coordination structures from1D to3Dframeworks. Complexes6and7show two different1D polymeric chains. Complex6isa1D zigzag chain, in which the3-dpyp ligand exhibits a bidentate coordination modewith a “U-shape” conformation, attaching to one side of the [Cu-1,3-BDC]nzigzag chain to build a binuclear ring. While complex7is a1D double strand chain linked by3-dpyp and1,3-BDC ligands. Six kinds of different2D layer structures (for complexes1,3,5,9-15and20-23) exhibit the (42·67·8)(42·6) topology for complex1, the(42·63·8)(42·6) topology for isostructural complexes3,12,14and22, the (44·62)topology for5,11,15and23, the (4·62)2(42·62·82) topology for complex9, the(42·67·8)(42·6) topology for10,20and21, the (64·8·10)(6) topology for complex13.Four kinds of different3D coordination frameworks can be observed for complexes2,4,8and16-19. Complex2reveals a3D polymeric framework with3-fold interpenetrating4-connected (65·8) CdSO4-like topology, the isostructural complexes4and8possess a(3·4·5)2(3·42·5·86)2(32·8·92·10)(42·82·102) topology, complex16displays a3-foldinterpenetrating3D α-Po framework, three isostructural complexes17-19are3Dframeworks with a CdSO4-like topology. In complexes1–23, the flexiblebis-pyridyl-bis-amide ligands adopt a μ2-bridging mode in1-3,5-7, and9-23(vialigation of two pyridyl nitrogen atoms) and a μ4-bridging coordination mode in4and8(via ligation of two pyridyl nitrogen atoms and two carbonyl oxygen atoms), which playan important role in the construction of final polymeric structures.2. By changing the different aromatic dicarboxylic acids auxiliary ligands, twenty-threeCu(II), Ni(II), Co(II), Zn(II) or Cd(II) complexes have been hydrothermally synthesized based onthe semi-rigid bis-pyridyl-bis-amide ligands3-bpah and4-bpah as main ligands. Theinfluences of coordination numbers and coordination modes of different metal ions, the3-bpah or4-bpah ligands and organic polycarboxylic acids ligands on the constructionof different complexes has been investigated.[Co(3-bpah)(1,4-BDC)(H2O)3](24)[Ni(3-bpah)(1,4-BDC)(H2O)3](25)[Cu(3-bpah)(1,4-BDC)](26)[Zn(3-bpah)(1,4-BDC)]·H2O (27)[Cd(3-bpah)(1,4-BDC)(H2O)](28)[Cd(3-bpah)(1,3-BDC)]·H2O (29) [Cu2(3-bpah)(1,3-BDC)2]·H2O (30)[Cu(3-bpah)(5-MIP)]·2H2O (31)[Ni(3-bpah)(5-MIP)]·H2O (32)[Co(3-bpah)(5-MIP)]·H2O (33)[Cu(3-bpah)(3-NIP)](34)[Cu(3-bpah)(1,4-NDC)(H2O)]·3H2O (35)[Cu2(3-bpah)(1,4-NDC)2]·(1,4-H2NDC)·3H2O (36)[Cu3(4-bpah)3(1,2-BDC)3(H2O)2]·4H2O (37)[Cu(4-bpah)(1,3-BDC)(H2O)](38)[Co(4-bpah)(1,3-BDC)(H2O)](39)[Ni(4-bpah)(1,3-BDC)(H2O)](40)[Zn(4-bpah)(1,3-BDC)(H2O)](41)[Cd(4-bpah)(1,3-BDC)](42)[Cu(4-bpah)(5-MIP)(H2O)](43)[Ni(4-bpah)(5-MIP)(H2O)]·H2O (44)[Co(4-bpah)(5-MIP)](45)[Cu(4-bpah)(3-NIP)]·H2O (46)The twenty-three complexes display different coordination features with1D chains,2D layers or3D frameworks. Complexes24,25,35and44show two kinds of different1D polymeric chains. Complexes24and25are isostructural and display the similar1Dinfinite chains, which each aromatic dicarboxylic anion coordinates to the metal ionthrough only one carboxyl oxygen atom, leaving the other oxygen atomsnon-coordinated and resulting in fish-bone chains. While complexes35and44are twosimilar1D double strand chains linked by N-donor and O-donor ligands. In complexes27-29,31,34,37-43,45and46, six kinds of different2D layer structures can be found:the (4·85)(4) topology for27and28, the (42·6·86·12)(42·6)(8) topology for31, the(12)(4·125)(4) topology for34, the (3·4·5·62·7)2(3·42·52·7) topology for37, the similar2D sql network with (44·62) topology for38-41,43and46, the (42·6)(43·6·84·102)(4) topology for42and45. Complexes26,30,32,33and36exhibit four kinds of different3D coordination frameworks: a4-connected (65·8) CdSO4-like topology for complex26,a new3D3-nodal topology with the Schl fli symbol (4·62)2(42·64)2(42·68·82·103) forcomplex30, two isostructural3D frameworks with a trinodal (2,3,5)-connected(42·6·84·102·12)(42·6)(8) topology for complexes32and33, a3D α-Po framework for36,in which the1,4-H2NDC ligands are inside the channels. In complexes24–46, thesemi-rigid bis-pyridyl-bis-amide ligands adopt a μ2-bridging mode in24-27,29,31-35,and37-46(via ligation of two pyridyl nitrogen atoms), a μ2-bridging coordination modein28and37(via ligation of one pyridyl nitrogen atom and one carbonyl oxygen atom),and a μ3-bridging coordination mode in30(via ligation of two pyridyl nitrogen atomsand one carbonyl oxygen atom), which play an important role in the construction offinal polymeric structures.