Three new Cu(Ⅱ)-Ln(Ⅲ) heterometallic coordination polymers based on two N-heterocyclic carboxylic ligands, {[LnCu(L1)2(L2)(H2O)2]·mH2O}n (Ln = La(1), Nd(2), Gd(3), m = 2 (for 1), 1 (for 2, 3), H2L1 = quinolinic acid, HL2 = nicotinic acid), have been synthesized and characterized. 1 has a two-dimensional (2D) layer structure with a Schlfli symbol of (44.62), while complexes 2 and 3 are isostructural and have three-dimensional (3D) structures with a Schlfli symbol of (3.4.5)2(32.42.52.614.74.83.9)(32.63.7) of 3-nodal net. Magnetic investigations suggest that antiferromagnetic coupling exists between NdIII and CuII in 2, while weak ferromagnetic coupling between GdIII and CuII in 3. The difference of magnetic properties between 2 and 3 has been discussed.
LIU SuiJun SONG WeiChao XUE Li HAN SongDe ZENG YongFei WANG LiFu BU XianHe
Two new Cu(Ⅱ) coordination polymers,[Cu(FDA)(BPY)(H2O)]n(1) and {[Cu(FDA)(BPY)(H2O)]·2H2O}n(2)(H2FDA = 2,5-furandicarboxylic acid,BPY = 2,2-bipyridine),have been synthesized and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR.Compound 1 crystallizes in monoclinic,space group P21/c,with a = 7.5915(15),b = 8.4050(17),c = 24.204(6) ,β = 99.05(3)°,V = 1525.1(6) 3,Dc = 1.706 g/cm3,C16H12CuN2O6,Mr = 391.82,F(000) = 796,μ(MoKα) = 1.470 mm–1,Z = 4,R = 0.0633 and wR = 0.1059 for 2389 observed reflections(I > 2σ(I)),R = 0.0738,and wR = 0.1098 for all data.Complex 2 belongs to triclinic space group P1 with a = 8.8660(18),b = 8.9112(18),c = 12.525(3) ,α = 88.41(3),β = 69.38(3),γ = 66.95(3)°,V = 845.2(3) 3,Dc = 1.681 g/cm3,C16H16CuN2O8,Mr = 427.85,F(000) = 438,μ(MoKα) = 1.342 mm–1,Z = 2,R = 0.0290 and wR = 0.0690 for 2767 observed reflections(I > 2σ(I)),R = 0.0329 and wR = 0.0706 for all data.Complexes 1 and 2 are both coordination polymers with one-dimensional chain structures bridged by the protonated FDA ligands,which are assembled into three-dimensional supramolecular structures through hydrogen bonding interactions and π-π packing interactions between the chains.
Three new CuⅡ coordination polymers,[Cu2(oba)2(H2O)(DMF)].3H2O(1),[Cu4(oba)4(DMF)4].4H2O.DMF(2) and [Cu2(oba)(hmp)2](3)(H2oba = 4,4'-oxybis(benzoic acid),Hhmp = 2-pyridine methanol,DMF = N,N'-dimethylformamide) were synthesized by solvothermal reactions and characterized by single-crystal X-ray diffraction.Both complexes 1 and 2 take three-dimensional(3D) three-fold interpenetrating PtS topology with 1D channels.In complex 3,Cu4 clusters were formed by the chelating hmp ligands,and then the clusters were further linked by oba ligands to form a 3D three-fold interpenetrating dia topology network.For 2,N2 sorption shows type I isotherm with BET surface areas of 562 m2 g-1 and Langmuir surface area of 747 m2 g-1,respectively.At 77 and 87 K,the hydrogen uptakes of complex 2 are 0.89 wt% and 0.57 wt%,respectively.Magnetic investigation showed the ferromagnetic coupling between CuII ions and very weak antiferromagnetic interaction between Cu4 clusters in complex 3.
ZHANG XiaoFeng,YANG Qian,ZHAO JiongPeng,HU Tong-Liang,CHANG Ze & BU Xian-He* Tianjin Key Laboratory of Metal & Molecule-based Material Chemistry
Three new cobalt complexes,{[Co5(tci)2(bimb)3(3-O)2(H2O)2]·3DMF·4H2O}n(1),{[Co3(tci)2(bib)]·2DMF·2H2O}n(2)and{[Co(Htci)(bpea)0.5]·H2O}n(3)(H3tci=tris(2-carboxyethyl)isocyanurate,bimb=4,4′-bis(imidazol-1-yl)biphenyl,bib=1,4-bis(imidazol-1-yl)benzene,bpea=1,2-bis(4-pyridyl)ethane,DMF=N,N′-dimethylformamide),have been successfully synthesized through the assembly of Co(II)ions,H3tci and different N-donor ligands,respectively.All complexes were structurally characterized by single crystal X-ray diffraction,elemental analyses,IR spectra,thermogravimetric(TG)analyses and X-ray powder diffraction(XRPD).Complex 1 exhibits a 3D three-fold parallel interpenetrated 3D→3D structure with(65·8)CdSO4topology.Complex 2 is built from[Co3(2-Ocarboxyl)2(CO2)4]clusters and linear bib ligands,displaying a two-fold parallel interpenetrated(3,8)-connected(43)2(46·618·84)topology,while complex 3 is a 3D pillar-layered structure involving an infinite–Co–(2-Ocarboxyl)(CO2)–Co–chain.The diverse structures of the three complexes indicate that the skeletons of different N-donor ligands play an important role in the assembly of such different frameworks.In addition,magnetic investigation indicates that besides spin-orbit coupling of Co(II)ions,there exist antiferromagnetic exchange interactions in Co5and Co3clusters of 1 and 2,respectively.
Coordination polymers (or metal-organic frameworks, MOFs), as one of the essences of crystal engineering and coordination chemistry, have attracted considerable atten-tion from chemists,
