Syntheses And Properties Of Copper/Cobalt Coordination Polymers Based On Bis-pyridyl-bis-amide Ligands And Organic Carboxylic Acids

In this thesis, a series of flexible bis-pyridyl-bis-amide ligands, namelyN,N′-bis(3-pyridyl)oxamide (L1), N,N′-bis(3-pyridyl)malonamide (L2),N,N’-di(3-pyridyl)succinamide (L3), N,N′-bis(3-pyridyl)adipamide (L4),N,N′-bis(3-pyridyl)heptandiamide (L5), N,N′-bis(3-pyridyl)octanediamide (L6) andN,N’-bis(3-pyridyl)sebacicdiamide (L7) have been selected as the main ligands anddifferent organic polycarboxylic acids [1,2-benzenedicarboxylate (1,2-H2BDC),1,3-benzenedicarboxylate (1,3-H2BDC),1,3,5-benzenetricarboxylate (1,3,5-H3BTC),5-aminoisophthalic acid (5-H4AIP),5-nitroisophthalic acid (H2NIPH),1,4-naphthalenedicarboxylic acid (1,4-H2NDC),1,4-cyclohexanedicarboxylic acid(1,4-H2CHDC), thiophene-2,5-dicarboxylic acid (H2TDC)] have been used as theauxiliary ligands to react with transition metal copper(II) or cobalt(II) ions underhydrothermal conditions. Thrity-two new complexes have been synthesized andcharacterized by elemental analyses, IR, powder X-ray diffraction and single-crystalX-ray diffraction. The TG, fluorescent properties, electrochemical behaviors andphotocatalytic activities of some coordination polymers have been studied.1. The L1-L7were used as main ligands and different organic polycarboxylicacids as auxiliary ligands to react with transition metal copper(II) ions underhydrothermal conditions. Twenty-two Cu(II) coordination polymers with differentstructural features: from one-dimensional (1D) to three dimensional (3D), have beensuccessfully synthesized and structurally characterized. The effect of the flexiblebis-pyridyl-bis-amide ligands with different–(CH2)n–spacers and organiccarboxylates on the sructures has been discussed.[Cu(L1)(1,2-BDC)](1)[Cu(L3)(1,2-BDC)]·H2O (2)[Cu(L4)(1,2-BDC)](3)[Cu(L6)(1,2-BDC)](4) [Cu(L7)(1,2-BDC)]·H2O (5)[Cu(L2)(1,3-BDC)(H2O)]·2H2O (6)[Cu(L3)(1,3-BDC)(H2O)](7)[Cu(L5)(1,3-BDC)(H2O)2]·2H2O (8)[Cu(L6)(1,3-BDC)(H2O)]·3H2O (9)[Cu2(L7)2(1,3-BDC)2(H2O)2]·7H2O (10)[Cu2(L6)2(5-AIP)2(H2O)]·6H2O (11)[Cu(L1)(HBTC)]·2H2O (12)[Cu(L2)(HBTC)](13)[Cu(L3)(HBTC)]·2H2O (14)[Cu(L4)(HBTC)(H2O)]·H2O (15)[Cu3(L7)(HBTC)2(H2O)5]·4H2O (16)[Cu(L3)(NIPH)](17)[Cu(L3)(1,4-NDC)]·3H2O (18)[Cu(L3)(1,4-chdc)]·3H2O (19)[Cu(L3)(1,4-chdc)]·H2O (20)[Cu(L3)(tdc)]·H2O (21)[Cu(L3)(tdc)]·2H2O (22)Complex1possesses a3D coordination network based on1D [Cu-1,2-BDC]nchains and [Cu–L3]nchains, which represents a CdSO4-type topology. Complex2exhibits a2D (2,4)-connected (4·124·14)(4) net. Complexes3-5have similarstructures and show2D networks with undulated sql topology. Complexes6-8and10have similar wave-like2D structures. Complex9displays a3D coordinationpolymeric architecture based on1D [Cu-1,3-BDC]nchains and [Cu–L6]nchains,which represents an intriguing3-fold interpenetrating framework with CdSO4-typetopology. It is similar to complex9, when1,3-BDC is replaced by5-AIP, another3-fold interpenetrating3D CdSO4-type coordination framework for compound11isobtained, which is constructed from three types of1D chains:[La–Cu–Lc]nchain,[Lb–Cu–Lb]nchain and [Cu-5-AIP]nchain. In complexes12-15, we selected1,3,5-HBTCas the auxiliary ligand. Complexes12and14are isostructural and exhibit a2Ddouble-layer framework with (3,5)-connected {42·67·8}{42·6} topology, then their2D double-layers are extended into3D supramolecular networks by π–π stackinginteractions or hydrogen bonding interactions. Complex13features aone-dimensional (1D)∞-like double-chain structure, which consists of a [Cu-HBTC]nchain and [Cu-L2]nmeso-helical chain. Complex15possesses a (2,4) undulatedhoneycomb (hcb) net. Complex16is a3-fold interpenetrating three-dimensional (3D)framework, which shows trinodal (2,3,3)-connected topology with the Schl fli symbolof (10·122)2(103)2(12). Complexes17-22are based on the same L3ligands and coppermetal ions, only change organic carboxylic acid and pH. When H2NIPH was used asthe auxiliary ligand, complex17is a2D coordination polymer based on tri-flexuralhelix chains (left-, right handed [Cu-L]nhelix chains, and left-handed Cu-NIPH helixchain). The synthetic method of18is similar to17except that1,4-NDC was replacedby H2NIPH, and the complex18is a2D (4,4) network. Compound19and20(21and22) were obtained from a one-pot reaction, respectively. Compound19contains raretwo types of left-, right handed [Cu-L3]nhelix chains, which are further connected by[Cu-1,4-chdc]nzigzag chains affording a2D polymeric framework. Complexes20-22possess similar uninodal2D square grid layer with44-sql topology constructed fromzigzag [Cu-L]nchains and linear [Cu-1,4-chdc]nor [Cu-H2tdc]nchains.2. By choosing the different organic carboxylic acid as auxiliary ligands, ten Co(II)complexes based on the flexible bis-pyridyl-bis-amide ligands with different–(CH2)n–spacers have been hydrothermally synthesized. The influences of coordination numbersand coordination modes of Co(II) ions, the flexible bis-pyridyl-bis-amide ligands withdifferent–(CH2)n–spacers and organic polycarboxylic acids ligands on theconstruction of different complexes has been investigated.[Co(L1)0.5(5-AIP)]·H2O (23)[Co(L2)(5-AIP)(H2O)2](24)[Co(L3)0.5(5-AIP)](25)[Co(L4)0.5(5-AIP)(H2O)]·2H2O (26)[Co(L5)(5-AIP)](27)[Co(L6)0.5(5-AIP)(H2O)]·2H2O (28)[Co2(L3)2(1,3-BDC)2]·4H2O (29)[Co(L6)(1,3-BDC)(H2O)2]·H2O (30)[Co2(L4)1.5(1,2-BDC)(μ2-OH)(μ3-OH)(H2O)]·H2O (31)[Co(L6)1.5(1,2-BDC)(H2O)](32) Complexe23is a2D double-layer framework with3,4-connected {63}{66}topology constructed from2D [Co(5-AIP)]nlayers and L1linkers. Complexe24possess1D chain-like structures derived from1D [Co(L2)]n‘’-like chain and1D[Co(5-AIP)]n‘V’-like chain. When the length of spacers for the N-donor ligand isfurther increased in25, a3,8-connected3D coordination framework with{42.6}2{44.610.79.85} topology was obtained. Two similar complexes26and28display a2D ladder layers base on the1D [Co(5-AIP)] open railroad-like chains andL4ligands. Complexe27displays a novel3-fold interpenetrating CdSO4-like networkconstructed by dinuclear {Co2} SBUs and two kinds of bridging ligands (L5and5-AIP). Complex29features a6-connected2-fold interpenetrated3D α-Po-relatedarchitecture. Complex30shows a2D (44) grid network with the sql topology, whichconsists of the1D zigzag [Co–L6]nchain and1D linear [Co-1,3-BDC]nchain.Complex31furnishes a3D coordination polymer based on bidentate bridging L4ligands and tetranuclear {Co4} SBUs, which represents a6-connected {412.63}topology. In complex32, the adjacent CoIIions are connected by L6ligands to form a1D chain with an alternating arrangement of L6ligands and Co2L2dinuclear loops.