Synthesis And Characterization Of Coordination Polymers Constructed By Flexible Carboxylic Acid Containing Quaternary Ammonium

Metal organic framework(MOFs),also known as metal coordination polymers(CPs),are crystalline materials constructed from metal ion bridged by organic ligand to form zero-dimension,one-dimensional,two-dimensional or three-dimensional structure.Metal organic framework(MOFs)are becoming one of the most rapidly developing fields in chemistry and materials science,not only because of their interesting network topology with high and permanent uniform porosity,pore size,large surface area,pore surface properties of adjustable,but also due to their potential application in gas adsorption and separation,luminescence,catalysis,proton transfer,sensing and so on.In this paper,the synthesized organic ligands N,N-bis[2'-carboxy(1,1'-biphenyl)-4-methylene]dimethylamine(HBCDMA)and N,N,N-tri[2'-carboxy(1,1'-biphenyl)-4-methylene]methylamine(H2TCMA)were used to react with transition metal and rare earth elements to produce fourteen coordination polymers.And these coordination polymers were characterized by X-ray single crystal diffraction TGA,MS,IRand XRD powder diffractometer.The synthesized coordination polymer as follows:(1){[Zn(BCDMA)(Cl)(H₂O)]_n}(2){[Zn(BCDMA)(H₂O)(HCOO)]}_n(3){[M(BCDMA)(CH₃COO)]}_n[M=Cd(3),Co(4),Mn(5)](6){[Mn₃(BCDMA)₃(H₂O)₆](NO₃)3(H₂O)2}n(7){{[Cu₄(BCDMA)₄(CH₃CH₂OH)2](NO₃)4}·[K(BCDMA)(H₂O)4]·(H₂O)2}n(8)[Co₂₄(?₃-O)₄(BCDMA)₄(?₃-OH)4(?₂-OH)4(NO₃)5(HCO₂)22(H₂O)10](HCO₂)(CH₃OH)2(H₂O)13](9){[Mn₂(TCMA)₂(H₂O)]}_n(10){[Ln(HTCMA)(TCMA)(DMF)]}_n[Ln=Tb(10),Eu(11),Ho(12),Er(13)](14){[Tb(TCMA)(NO₃)]}_nComplex(1)and Complex(2)are one-dimensional chain with zig-zag structure constructed by a ligand bridged two metal ions.Complex(3),(4)and(5)are allomerism.They are one-dimensional chain structure with double helixes which are bridged by carboxylic acid oxygen with ?1,?1 mode.Complex(6)is an one-dimensional chain structure in which the building blocks[Mn₃(CO₂)6]are bridged by the carboxylate radical of ligand to form as a node.Between the nodes are connected by three ligands in the same direction with screw mode.Complex(7)is consist of {[Cu₄(BCDMA)₄(CH₃CH₂OH)2](NO₃)4 and[K(BCDMA)(H₂O)4]·(H₂O)2}.The {[Cu₄(BCDMA)₄(CH₃CH₂OH)2](NO₃)4} is one-dimensional chain structure constructed by four ligands bridged four Cu2+ions with paddle-wheel[Cu2(CO₂)4]mode to form a spiral cage in same direction in which look like as train bridged by C u-O to form.The axial position of paddle-wheel[Cu2(CO₂)4]structure was dominated by ethanol.[K(BCDMA)(H₂O)4]is a one-dimensional chain obtained a ligand bridged two K ions.Comples[Co₂₄(?₃-O)₄(BCDMA)₄(?₃-OH)4(?₂-OH)4(NO₃)5(HCO₂)22(H₂O)10](HCO₂)(CH)3(OH)2(H₂O)13(8)is formed by hydrolysis of DMF,The Co2+ ions are bridged by HCO₂-,NO₃?and OH-resulting in a Co₂₄ cluster which is stabilized by four ligands BCDMA.Complex {[Mn₂(TCMA)₂(H₂O)]}_n(9)is a two-dimensional structure constructed by ligand TCMA with a fan configuration bridging metal ions.Complexes {[Ln(HTCMA)(TCMA)](DMF)}n[Ln=Tb(10),Eu(11),Ho(12),Er(13)]are allomeric.They are a mesomerically double chain constructed by ligands with a two-connection mode bridging metals.In these complexes,ligands take as two types,of which one is all carboxylic groups deprotonized but another only two carboxylic groups deprotonized.Complex(14)is a two-dimensional structure constructed by ligand TCMA with a fan configuration bridging Tb³⁺ions.