The hydrothermal reaction of Zn(NO3)2·4H2O, cyclohexane-1,2,3,4,5,6-hexacarboxylic acid hydrate (H6LI·H2O, cis-conformation LI: a,e,a,e,a,e) and 2,2'-bpy yielded a new coordination polymer [Zn2(H2LII)(2,2'-bpy)]·2H2O(trans-conformation LII: e,e,e,e,e,e), which was characterized by single-crystal X-ray diffraction, elemental analysis, IR and XRPD(X-ray powder diffraction). This complex crystallized in the triclinic system, with P1 space group and parameters a=0.66922(5) nm, b=0.97291(8) nm, c=1.22184(9) nm, α=99.0020(10)°, β=99.1300(10)°, γ=99.1910(10)°, V= 0.76176(10) nm3 and Z=2. The structure is a three-dimensional supramolecular network based on linear coordination chains through π-π stacking and hydrogen bonding interactions. The confromation of the starting ligand H6LI transfromed to the H2LII. The complex emits strong luminescence at room temperature.
The hydrothermal reactions of Ni(Ⅱ), 1,2,3-benzenetricarboxylic acid (1,2,3-H3btc) and 4,4'-bipyfidine (4,4'-bpy)/1,2-bis(4-pyridyl)ethane (bpa) yield two layered nickel(II) coordination polymers, [Ni2(l,2,3-btc)(OAc)- (4,4'-bpy)2(H20)]o2H2O (1) and [Ni(ip)(bpa)] (2) (ip=isophthalate), respectively. Both complexes are 2-D coordi- nation network based on 1-D Ni-carboxylate chains. The 1,2,3-btc ligand adopts 3-bridging mode in complex 1, but transformed to isophthalate (ip) ligand through decarboxylation in 2. The formation of the two complexes indicates that hydrothermal conditions and in-situ ligand reaction have significant effect on constructing coordination polymers.
The hydrothermal reaction of Cd(OAc)2·2H2O, 4,4'-bpy and cyclohexane-1,2,4,5-tetracarboxylic acid (H4L) yields a three-dimensional (3D) coordination porous framework [Cd2LI(4,4'-bpy)1.5(H2O)2]n·2nH2O, which was characterized by single-crystal X-ray diffraction (MoKα radiation, λ = 0.71073), elemental analysis and IR. This complex crystallizes in the monoclinic system, space group C2/c with a = 25.951(3), b = 11.6618(12), c = 20.046(2) A, β = 114.863(2)o, V = 5504.4(10)A^3, Z = 8, Dc = 1.900 g/cm^3, Mr = 787.30, μ = 1.615 mm^-1, F(000) = 3128, the final R = 0.0978 and wR = 0.1780. The structure of the complex is a 3D coordination Cd-carboxylate framework consisting of 1D hexagonal channels along the c-axis filled with the bridging 4,4'-bpy ligands. The 4,4'-bpy ligands with two kinds of conformations are located alternately in the channels through coordination and hydrogen interactions to support the whole porous framework, in which the conformation-flexible cyclohexane-1,2,4,5-tetracarboxylate ligand adopts the I (e,a,a,e) conformation and acts as a pentadentate ligand to connect five Cd(Ⅱ) atoms via the carboxylate groups in different coordination modes.