Three new Cu（Ⅱ）-Ln（Ⅲ） heterometallic coordination polymers based on two N-heterocyclic carboxylic ligands, {[LnCu（LI）2（L2）（H2O）2]· mH20},, （Ln = La（1）, Nd（2）, Gd（3）, m = 2 （for 1）, 1 （for 2, 3）, H2L1 = quinolinic acid, HE2 = nico- tinic acid）, have been synthesized and characterized. 1 has a two-dimensional （2D） layer structure with a Schlifli symbol of （44.62）, while complexes 2 and 3 are isostructural and have three-dimensional （3D） structures with a Schlafli symbol of （3.4.5）2（32.42.52.6]4.74.83.9）（32.63.7） of 3-nodal net. Magnetic investigations suggest that antiferromagnetic coupling exists be- tween NdIn and Cun 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）（H20）]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） A, β = 99.05（3）°, V= 1525.1（6） A3, Dc = 1.706 g/crn3, C16HI2CuN206, Mr = 391.82, F（000） = 796, μ（MoKa） = 1.470 mm-l, Z = 4, R = 0.0633 and wR = 0.1059 for 2389 observed reflections （1 〉 2a（I））, R = 0.0738, and wR = 0.1098 for all data. Complex 2 belongs to triclinic space group PI with a = 8.8660（18）, b = 8.9112（18）, c = 12.525（3） A, a = 88.41（3）, β = 69.38（3）, γ = 66.95（3）°, V = 845.2（3） A3, Dc = 1.681 g/cm3, CI6HI6CuN2Os, 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.
Three new cobalt complexes, {[Co5（tci）2（bimb）3（μ3-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-l-yl）biphenyl, bib = 1,4-bis（imidazol-l-yl）benzene, bpea = 1,2-bis（4-pyridyl）ethane, DMF = N,N＇-dimethylformamide）, have been successfully synthesized through the assembly of Co（If） 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） CdSO4 topology. Complex 2 is built from [Co3（μ/2-Ocarboxyl）2（CO2）4] clusters and linear bib ligands, displaying a two-fold par- allel interpenetrated （3,8）-connected （4^3）2（4^6.6^18·8^4） topology, while complex 3 is a 3D pillar-layered structure involving an in- finite -Co-（μ2-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 indi- cates that besides spin-orbit coupling of Co（II） ions, there exist antiferromagnetic exchange interactions in Co5 and Co3 clus- ters 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,
