Design,Synthesis And Properties Of Coordination Polymers Based On 4-substituted Triazole And Multicarboxylate Ligands

Coordination polymers materials have drawed wide attention due to the designable structure and their potential application values in many fields.Nitrogen hetercyclic and multicarboxyl ate mixed ligands system are very effectively in the design and synthesis of coordination polymers.In this work,1,4-bis(1,2,4-triazole-4-ylmethyl)benzene(btrb)and 1,4-bis(1,2,4-triazole-4-ylmethyl)-2,3,5,6-tetramethylbenzene(tmtb)were used as the main ligands,Co(?)/Cu(?)/Zn(?)/Cd(?)ions were used as the central metal ions.A series of coordination polymers were designed and synthesized by changing multicarboxylate ligands and synthesis condition.Brief introduction is shown as below:1.Three coordination polymers based on tetranuclear Co(II)clusters{[Co4(OH)2(adc)6(H20)5][Co2(OH)(btrb)]2·8H2O}n(1),{[Co4(OH)2(btrb)(nip)3(H2O)3]·4H2O}n(2·4H2O)and {[Co4(OH)2(btrb)(1,3,5-btc)2(H2O)2]·9H2O}n(3·9H2O)were synthesized by a hydrothermal method.By the regulation of the multicarboxylate ligands,1-3 are all based on the[Co4(?3-OH)2]building units and the connection numbers increase from 4 in 1 to 6 in 2 and then 8 in 3.Magnetic measurements reveal that 1-3 exhibit antiferromagnetic properties.1-3 show good activities in the degradation of methylene blue(MB).Besides,1-3 are potential electrode materials.2.Three Co(?)coordination polymers[Co(tmtb)0.5(btec)0.5]n(4),[Co3(tmtb)(1,3,5-btc)2]n(5)and {[Co4(OH)2(tmtb)2(1,2,4-btc)2(H2O)6]·7H2O}n(6)were synthesized by a hydrothermal method.4-6 are good photocatalysts for the degradation of MO.The nuclear numbers of Co(II)clusters building units increase form binuclear in 4 to trinuclear in 5 and then tetranuclear in 6 by the regulation of the multicarboxylate ligands.3.Three coordination polymers[Cu2(OH)(btrb)0.5(2,2'-bpdc)(2,2'-Hbpdc)]n(7),{[Cu2(OH)(btrb)(1,3,5-btc)]·4H2O}n(8·4H20)and {[Cu2(OH)(btrb)(sip)]·2H20}n(9·2H20)based on tetranuclear Cu(II)clusters were synthesized by a hydrothermal method.7-9 are all based on the[Cu4(?3-OH)2]building units.The structure dimensions of coordination polymers are tuned by multicarboxylate ligands and increase form 1D of 7 to 2D of 8 and then 3D of 9.7-9 show good activities for degradation of MO,MB and RhB.4.Eleven Cd(?)coordination polymers{[Cd(btrb)(H20)4][Cd2(btrb)(btec)(H2O)2]2(OH)2·5H2O}n(10·(OH)2·5H2O),{[Cd(btrb)0.5(3,3',4,4'-bptc)0.5]·H2O}n(11·H2O),{[Cd3(btrb)(1,3,5-btc)2]·3H20}n(12·3H20),{[Cd(btrb)(ip)(H20)]·H20}n(13),{[Cd(btrb)(MeOip)]·H2O}n(14),{[Cd2(btrb)2(1,2-bdc)2]·3H20}n(15),{[Cd2(btrb)(2,2'-bpdc)2]2·11H2O}n(16),{[Cd(btrb)(2,2'-bpdc)]·H2O}n(17),{[Cd2(btrb)(adc)2(H20)]·4H20}n(18·4H20),{[Cd(btrb)(adc)]·2H20}n(19)and {[Cd5(btrb)4(1,2,3-btc)3][Cd(1,2,3-btc)(H2O)4]·30.5H2O}n(20·30.5H2O)were synthesized using btrb and nine kinds of multicarboxylate ligands.10 is the first 1D+3D?3D polythread structure with the electroneutral 3D motif,and the 3D motif shows an unreported(4,4,4,4)-connected blil or a rare mot topology.11 shows an unreported(4,5,6)-connected topology named as bli2.12 shows an unreported(3,8)-connected 3D network named as bli3.10-20 show different luminescence properties.The diverse topology of 10-20 demonstrate that unprecedented and intriguing topologies of coordination polymers can be adjusted by tuning the synthesis conditions using 4-substituted triazole and multi carboxylate co-ligands.5.Seven coordination polymers {[Co(btrb)(MeOip)]·H2O}n(21),[Co(btrb)0.5(NH2ip)(H2O)]n(22),[Cu(btrb)0.5(NH2ip)(H2O)]n(23),{[Co3(btrb)i.5(Meip)3(H2O)]·3H20}n(24·3H20),[Zn(btrb)0.5(1,4-bdc)]n(25),[Zn2(btrb)0.5(Meip)2]n(26)and {[Zn2(OH)(btrb)0.5(1,3,5-btc)(H2O)]·4H2O?(27·4H2O)were synthesized using btrb and five multicarboxylate ligands.The diverse structure of 21-27 demonstrate that the 4-substituted triazole and multicarboxylate co-ligands system are benefit to design and regulate the structures of coordination polymers.