| This work designed and synthesized three semi-rigid ligands:1,3-bis(imidazol-1-yl-methyl)benzene(L1),1,3-bis(triazole-1-yl-methyl)benzene(L2)and 1,4-bis(imidazol-1-yl-methyl)benzene(L3).Seventeen complexes were constructed by these three ligands connecting with transition metals,in which fifteen complexes were coordination complexes,and the other two were hydrogen bonding supramolecular compounds.The products are characterized by elemental analysis,IR spectroscopy,PXRD,TGA and X-ray crystallography.Six metal-organic coordination complexes with supramolecular extended structures were synthesized by using the L1,L2 and L3 ligands to coordinate with link transition metals:[Mn(Ll)2(H2O)2](NO3)2(1),[Mn(L1)2Cl2](2),[Mn(L1)2](NO3)2·2(H2O)(3),[Zn(L1)2](NO3)2·(H2O)(4),[Cd(L2)2(NO3)2](5)and[Zn(L3)Cl2](6).Complexes 1-4 were synthesized by using L1 ligand,in which the complexes 1 and 2 bear the six coordinated Mn ions as the coordination centers and show 1D chain structures.Complexes 3 and 4 have the four coordinated Zn ions as the coordination centers.Complex 3 shows nano-scale ID pore structure,while complex 4 exhibits double-helical chains structure.Complex 5 was built up by L2 and Cd ion,which has a 1D chain structure similar as complex 2.Complex 6 was constructed by L3 and Zn ion,showing 1D wavelike chain structure.Four metal-organic coordination complexes and one hydrogen-bonding supramolecular compound were synthesized by L1,carboxylic acid and transition metals:[Co(Ll)(m-BDC)](7),[Ni(L1)(m-BDC)](8),[Zn2(L1))(p-BDC)2](9),[Ni(L1)(HBTC)]·H2O(10)and[H2L1][(H3BTC)2][(H2BTC)2](11).In complexes 7 and 8,the m-phthalic acid(m-BDC)serves as the auxiliary ligand.Complex 7 has a Co ion as the coordination center,and exhibits(4,4)-connected 2D network,while complex 8 has a Ni ion as the coordination center and shows a 5-connected uninode bnn-type 3D structure.The p-phthalic acid(p-BDC)was used to synthesize the complex 9.The(3,4)-connected mog-type 3D structure was obtained in 9,and finally formed 2-fold interpenetrated mog-typc framework.The structural difference between 8 and 9 should be caused by the auxiliary ligands with different configurations.The trimesic acid(H3BTC)was utilized to prepare complexes 10 and 11.In complex 10,the H3BTC acts as the bidentate ligand to link the transition metal atoms forming double-helical chain structure.Furthermore,the hydrogen bonds conncet the 1D chains into 3D supramolecular structure.However,the complex 11 shows an interesting double sheets structure,which is formed by the protonated L1 ligand,H3BTC and H2BTC.Five polyoxometalate-templated metal-organic coordination complexes and one polyoxometalate-based hydrogen bonding compound were synthesized by L1 or L2 ligands reacting with the Cu ions:[CuI4L24][PW12O40](12),[CuI2L2]2[Mo8O26](13),[CuI4(L1)4][W10O32](14),[(H2L1)2][Mo8O26](15),[CuI4(L2)4][SiW12O40](16)and[CuI4(L2)4][Mo8O26](17).Complexes 12-15 were built up by L1 moleculs.Among them,the complex 12 has[PW12O40]3-ion as the template with an interesting rotaxane structure,and the Cu…Cu interactions links these rotaxanes to form 3D framework.Complex 13 shows(3,4,6)-connected novel 3D structure with Schlafli symbol of(4·6·8)2(42·64·83·102·123)(44·62)2.In complex 14,the[PW12O40]3-ions decomposed at low pH condition and formed the[W10O32]4-ions.The[W10O32]4-ions induce the complex 14 forming 1D->2D self-interpenetrated structure.Complex 15 bears 3D supramolecular structure formed by L1 ligands and[Mo8O26]4-ions via hydrogen bonds and π-π interactions.Complexes 16 and 17 were constructed by L2 ligand and[SiW12O40]4-or[Mo8O26]4-ions.Complex 16 has a shelf-like 2D structure,while the complex 17 shows 2D network parallelled to the be plan.In addition,the luminescent,magnetic and electric properties of some complexes were also studied. |
PDF Full Text Request