Disign,Syntheses And Properties Research Of Coordination Polymers With Triazole Ligands

Nitrogen atoms of the triazole ligands have the strong coordination ability,which can coordinate with metal atoms to form the stable and varied coordination polymers.The varied spatial structures of the transition metal coordination polymers make them have unique properties.They had exhibited the wide application properties in gas adsorption,chiral separation,control the size of nano pore,luminescent sensors detecting cations,anions and small organic molecules,DNA sensing platform,catalysis,magnetic materials.Two mainly ligands including the flexible bistriazole ligand 1,2-bis(1,2,4-triazol-1-ylmethyl)benzene(obtz),the rigid bistriazole ligand 1,3-bis(1,2,4-triazol-4-yl)benzene(mbtx),and the flexible bistriazole ligand 1,2-bis(4-H-1,2,4-triazol-1-ylmethyl)benzene(otrb)were adopted to constructing the coordination polymers.Triazole ligands btre?abit?bth?bte?ttmb were also coordinated with carboxylic acid ligand 5-I/Br-H2bdc to synthesing the transation metal coordianation polymers.Thirty-eight coordination polymers have been synthesized and characterized.The research on luminescence and photocatalytic properties of some coordination polymers have been investigated.Part One:Five Cd(II)coordination polymers have been synthesed based on obtz,{[Cd2(obtz)2(btec)(H2O)2]·3.5H2O}n(1),{[Cd2(obtz)(Meip)2]·H2O}n(2),{[Cd3(obtz)(1,2,3-btc)2(H2O)]·0.5H2O}n(3),{[Cd5(obtz)2(nbdc)4(?3-OH)2]·2H2O}n(4),{[Cd(obtz)(ndc)]·0.5H2O}n(5).1 features the 3D metal-organic structure,topological symbol is(62·8·103)2(63 103).2 is the unusual(4,5)-connected 3D framework with the topological symbol(44·62)(46-84-82).3 is a new structure connected by polynuclear.4 features the 4-connected sql 2D network based on the five nuclear cluster[Cd5(?3-OH)2]n.5 is the 2D network.Coordination polymer 1,2,3,5 all exhibit strong luminescence intensity.The luminescence of 1,2 in different organic solvents(acetonitrile,ethanol,methanol,nitrobenzene)were investigated.Luminescent intensities of 1,2 gradually decreased with the increasing concentraton of nitrobenzene.The high quenching efficiency of 1 is up to 98.2%only at the concentration of NB is 160 ppm.The quenching efficiency of 2 is up to 92.7%at the concentration of NB is 750 ppm.It's obviously 1,2 can be as high efficient luminescent sensitive probe for nitrobenzene.Part Two:Transition metal Cu(?)and Ni(?)coordination polymers have been synthesed {[Cu(obtz)2(H2O)2]·[Cu2(obtz)2(sip)2]·5.5H2O}n(6),[Cu(obtz)(nip)]n(7),[Cu2(obtz)2(tdc)2]n(8),{[Ni2(obtz)2(tdc)2(H2O)]·2H2O}n(9),[Cu4(OH)2(otrb)2(sip)2]n(10).6-8 are the 2D network.7 is the 2D(4,4)-network?3D polycatenated framework by intermolecular interaction between two adjacent layers.10 exhibits the 3D network based on nuclear cluster[Cu4(?3-OH)2]n 6-8 as the photocatalyst by degradating methy orange(MO)under ultraviolet lamp.The degradation efficiency of 8 is up to 91.7%in 140 mins.10 exhibits excellent photocatalytic activity for the degradation of MO,Rhodamine B(RhB)and Methylene Blue(MB),the degradation efficiency is up to 94.4%,86.6%,91.2%,respectively.Part Three:Eight Co coordination polymers {[Co(obtz)2(fum)]·2H2O}n(11),{[Co2(obtz)2(tdc)2(H2O)]·2H2O}n(12),[Co(obtz)(Meip)]n(13),[Co(obtz)(1,3-bdc)]n(14),[Co(obtz)(1,4-bdc)(H20)]n(15),[Co(obtz)(OHbdc)]n(16),[Co(obtz)(adc)]n(17),[Co(obtz)(Brbdc)]n(18)have been synthesed.11 is the usual 2D network MONTs.12-14 all feature the 2D network.15 features the polycatenated 2D(4,4)-network.16 and 18 are the 1D chain.17 is the chiral(4,4)-connected 2D network.11,13,14,15,16,17 exhibit the photocatalytic activity for the degradation of MO.Part Four:Transition metal Zn(?),Mn(?)coordination polymers have been synthesed,{[Zn(obtz)(1,3-bdc)]·0.5H2O}n(19),{[Zn(obtz)(OH-bdc)]·3H2O}n(20),{[Zn(obtz)(ndc)]n(21),{[Mn(obtz)(1,2-bdc)]·H2O}n(22),{[Mn(obtz)(1,3-bdc)]·0.5H2O}n(23),[Mn(obtz)(OHbdc)]n(24),[Mn(obtz)(I-bdc)]n(25).19 and 20 feature the 1D MONTs.Nitrogen adsorption and desorption of 19 is investigated.21,25 are 2D network.22-24 are the 1D chain structure.19-24 all exhibit strong fluorescence intensity.19,22 exhibit the photocatalytic activity for degradation of MO.Part Five:Four Transition metal coordination polymers have been synthesed,which is based on the rigid ligand mbtx.{[Cu3(OH)2(mbtx)(nip)2]·H2O}n(26)exhibits the 3D network based on the three nuclear cluster[Cu3(?3-OH)2]n.[Cu2(OH)(mbtx)(sip)(H2O)2]n(27)is 2D network.{[Co2(mbtx)(tdc)(H2O)6]·(tdc)·4H2O}n(28)is the 1D chian.{[Zn5(OH)2(mbtx)2(nip)4(H2O)3]·3H2O}n(29)is the 2D network.26,27 are the excellent photocatalyst by improving degradation efficiency of organic dyes(MO,RhB and MB).Part Six:Applying triazole ligands btre,abit,bth,bte,ttmb with 5-I/Br-H2bdc to forming coordination polymers,{[Zn(btre)(Ibdc)]·2.75H2O}n(30),{[Zn2(abit)(Ibdc)2]·H2O}n(31),[Cd2(bth)(Ibdc)2(H2O)]n(32),{[Zn(bte)(Brbdc)(H2O)]·H2O}n(33),[Zn(ttmb)(Brbdc)]n(34),[Zn(ttmb)(Ibdc)]n(35),[Cu(ttmb)(Ibdc)]n(36),{[Mn(ttmb)(Ibdc)(H2O)2]·3H2O}n(37),{[Cd(ttmb)(Ibdc)]n(38).30 and 33 feature 1D MONTs,which may be contributed that bte,btre easily coordinated with Zn(II)to form 18-connected ring.The 5-substituent benzene carboxylic acid act as the connected function.31,36,38 are the 3D network,36 has the similar structure with 38.32 features the 3D porous metal-organic structure.34,35 are 2D(4,4)network.37 is the mononuclear structure.30,31,32,34,35 have the strong luminescence intensity.