Feng-Yun Cui

Structural variability of Cd(II) and Co(II) mixed-ligand coordination polymers: effect of ligand isomerism and metal-to-ligand ratio

A series of seven mixed-ligand coordination polymers, namely {[Cd4(H2L1)4(suc)4]·3H2O}n (1), {[Cd4(H2L1)3(suc)4]·5H2O}n (2), {[Cd2(HL1)2(suc)]·8H2O}n (3), {[Cd(H2L2)(suc)]·3H2O}n (4), {[Cd(H2L3)(suc)]·3H2O}n (5), {[Co(H2L1)(chdc)(H2O)]·H2O}n (6), {[Co(H2L2)(chdc)(H2O)]}n (7) have been produced by the reaction of three 2-amino-4,6-dipyridylpyrimidine isomers (H2L1, H2L2, H2L3) and secondary ligand 1,4-succinic acid (H2suc) or 1,4-cyclohexanedicarboxylic acid (H2chdc) with Cd(II) and Co(II) salts under hydrothermal conditions. All these compounds have been structurally determined by elemental analysis, IR and single-crystal X-ray diffraction. The three isomers are introduced in a mixed-ligand system for the first time. For the H2L1–H2suc–Cd(II) system, it is found that the structures of compounds 1–3 exhibiting a 1-D double-chain, a rare 1-D quadruple nano-chain and a 2-D network with (6,3) topology, respectively, are influenced by the ratio of metal-to-ligand. When H2L2 and H2L3 were used instead of H2L1, two 1-D chains (compounds 4 and 5) were obtained. Although they have the same molecular formula and structure motif, their supramolecular networks constructed by hydrogen-bondings and π–π stacking interactions are different. When H2L1 and H2L2 were introduced into the Co(NO3)2–H2chdc system, compounds 6 and 7 were successfully isolated, and display a zigzag chain and a helical chain, respectively. Interestingly, the cis- and trans-conformations of H2chdc were separated completely in the two compounds. The results reveal that both the coordination structure and the supramolecular assembly could be directed by the ligand isomers. Furthermore, several intriguing water clusters have been observed in these mixed-ligand compounds, such as a novel (H2O)10cluster in 2, a 2-D water net formed by (H2O)8clusters in 3, a 1-D undulated water chain in 4 and a chair-shaped (H2O)6cluster in 5. The solid-state properties of compounds 1–7 such as thermal stability and fluorescence have also been investigated.

pH-Dependent syntheses of copper–quinoxaline–polyoxotungatate hybrids: variable role of Keggin-type polyanion in different pH conditions

Four new hybrids based on the Keggin-type polyoxometalate, formulated as (Hbm)3(PW12O40)·4H2O (1) (bm = benzimidazole, which is synthesized in situ by quinoxaline), [Cu6(qx)9(PW12O40)2] (2), [Cu3(qx)5(PW12O40)(H2O)] (3) and [Cu4(qx)4(HPCuIIW11O39)]·1.5H2O (4) (qx = quinoxaline), were hydrothermally synthesized and structurally characterized by routine techniques and single-crystal X-ray diffraction. In 1, the [PW12O40]3− (PW12) clusters only act as counteranions and combine with the protonated organic ligand by electrostatic interactions. In 2, a 63 topological 2D layer is formed with the PW12 as the template. In 3, the PW12 anions link with four metal–organic chains via Cu–O weak interactions to construct a 3D framework. In 4, the Cu(II)-substituted Keggin unit as a hexadentate inorganic ligand coordinates with four Cu(I) ions from metal–organic chains and two O atoms from neighboring POMs to form a sandwich-like 2D layer. The structure difference of compounds 1–4 reveals that the self-assembly process is pH-dependent and the Keggin-type POM plays different role in different pH conditions.

Syntheses, structures, and magnetism of {V15M6O42(OH)6(Cl)} (M = Si, Ge)

Two [V15M6(OH)6O42(Cl)]7− (M = Si for 1, Ge for 2) cluster anions with protonated amines as counterions have been synthesized under hydrothermal conditions and characterized by FT-IR, energy dispersive spectroscopy, XPS, powder X-ray diffraction, thermogravimetric analysis (TGA), elemental analysis, and single-crystal X-ray analyses. Both compounds consist of {V15M6O42(OH)6(Cl)} (M = Si for 1, Ge for 2), which are derived from {V18O42} by substitution of three {VO5} square pyramids with three {Si2O5(OH)2/Ge2O5(OH)2} units. It represents the first example of cage-like polyoxovanadates (POVs) containing three (Si/Ge)2O5(OH)2 units. There are extensive hydrogen bonding interactions between POVs and organoamines in 1 and 2. Compound 1 presents a close-packed layer aggregate, while 2 exhibits the packing of six-membered rings with a 1-D channel. Magnetism measurements demonstrate the presence of strong antiferromagnetic interaction between VIV centers in 1.

Symmetry breaking of α-[H2W12O40](6-) depends on the transformation of isopolyoxotungstates.

Two enantiotopic 1D chain compounds, [Cu3(L1)3(H2O)2(H2W12O40)]·4H2O (1a,b; L1 = 2-(4,6-bis(pyridin-2-yl)pyridin-2-yl)pyridine), crystallizing in the chiral space group P212121 were prepared and spontaneously resolved in the absence of any chiral source. Interestingly, compounds 1a,b can be prepared from a [W7O24](6-) aqueous solution, [(n-C4H9)4N]4[W10O32], or Na10[H2W12O42], but when [H2W12O40](6-) aqueous solution was the starting material, the achiral compound [CuL1]2[H4W12O40]·5H2O (2) was obtained. When a terpyridine ligand (L2) having a coordination mode similar to that of L1 was used, the mesomeric dimer [Cu3(L2)3(H2O)(H2W12O40)]2·4H2O (3) was obtained from [W7O24](6-) aqueous solution or Na10[H2W12O42], but from [H2W12O40](6-) aqueous solution only compound [Cu2(L2)2Cl2]2[W10O32] (4) was isolated. It is notable that in compounds 1a,b and 3 the symmetry of the α-[H2W12O40](6-) cluster is broken by asymmetric coordination with metal-organic units in a similar mode. As the asymmetric subunit based on a tridecorated [H2W12O40](6-) cluster can be obtained from several isopolyoxotungstate sources except for [H2W12O40](6-), we speculate that the symmetry breaking of α-[H2W12O40](6-) depends on the transformation of isopolyoxotungstates. Furthermore, during the transformation a possible reaction intermediate as the precursor for 1a,b, compound [Cu3(L1)3(H2O)3(H4W11O38)] (5), has been presented and characterized by density functional theory (DFT) calculations.