A family of copper coordination polymers containing different N-heterocyclic ligands, namely [Cu(CN)(dmpyz)]_n (1),[Cu₂(CN)₂(imz)]_n (2), [Cu₃(CN)(trz)₂]_n (3), [Cu₆(CN)₆(dmtrz)₃]_n(4), [Cu₂(CN)(5-metta)]_n (5), [Cu₂(CN)(5-phtta)]_n (6), and {[Cu₆(CN)₆(dmtrz)]₂[Cu₂(CN)₂(dmtrz)₂]}_n (7) has been prepared and structurally characterized by X-ray crystallography. The crystal structures of 1 and 2 are 1D chain frameworks. Compound 3 is a twofold interpenetrating 2D supramolecular framework in which the cyanide groups act as bridging ligands to link the copper centers into an unusual bilayer motif with large channels. Compounds 4–6 all possess 3D networks. Compound 4 is constructed by two parts: 2D rectangular-grid layers and {Cu₂(CN)₂(dmtrz)₂} building blocks. Compound 5 is built up by X-shaped chains that connect each other in an ABAB arrangement to generate the3D network. The structure of 6 is a 3D network includingone-dimensional square-grid channels, with a shortest Cu2···Cu2A (A: –x + 1, –y + 1, –z) distance of about 2.347(1) Å. Compound 7 features a peculiar 3D + 1D network in which 1D guest metal-organic polymer chains are filled in an unusual 3D architecture constructed by double helical host tubes. Compounds 1–7 show a systematic variation in dimensionality from 1D to 3D to 3D + 1D. The luminescence properties of these compounds have been also studied. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Hydrothermal reactions between 2,6-naphthalenedicarboxylic acid (H₂NDC), 1,10-phenanthroline (1,10-phen) or 2,2′-bipyridine (2,2′-bpy), and transition metal acetates give rise to four coordination polymers, namely [Cu₃(NDC)₃(2,2′-bpy)(H₂O)₂]_n·nH₂O (1), [Cu(NDC)(1,10-phen)]_n (2), [Zn(NDC)(1,10-phen)]_n (3), and [Zn₄(OH)₂(NDC)₃(2,2′-bpy)₂]_n (4), which show different two-dimensional layered architectures. Compound 1 consists of three kinds of polymeric chains that are interconnected to form an unusual two-dimensional layered motif, while compound 4 features a two-dimensional honeycomb network structure with a noninterpenetrating ABCDABCD packing pattern. Compounds 2 and 3 show a two-dimensional grid-type framework but have different space-filling styles. The magnetic properties for 1 and 2 and the solid-state emission spectra of 3 and 4 have also been studied. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

The hydrothermal reaction of Cu(NO₃)₂·3 H₂O, K₃Fe(CN)₆, and 1,10-phenanthroline (1,10-phen) or 2,2'-bipyridine (2,2'-bpy) gives rise to the three one-dimensional helical-chain complexes [Cu₂Fe(CN)₄(1,10-phen)₃]_n·0.5n H₂O (1), [Cu₃(CN)₃(1,10-phen)₃]_n (2), and [Cu₃(CN)₃(2,2'-bpy)₃]_n (3), and the two-dimensional layer complex [Cu₃Fe(CN)₅(2,2'-bpy)₂]_n (4). The structure of 1 contains a cyanide-bridged Cu^I···Fe^II···Cu^I chain in which the two copper and one iron centers exhibit different coordination environments. The structures of 2 and 3 are both monometallic. Complex 4 is constructed alternately from fused 6- and 14-metal-membered nonplanar centrosymmetric rings that form a 2D layer architecture. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

The three-dimensional polymeric compound [Cu₄V₂(OH)₂O₈] (1) has been synthesized by the hydrothermal reaction of sodium vanadate and copper acetate in an aqueous solution basified with a 35% aqueous ammonia solution. Detailed experiments suggest that pH values within the range 8.5−11.3 are best for the formation of crystals of compound 1. X-ray diffraction analysis reveals that the structure of 1 is a three-dimensional polymer constructed from wave-like polymeric oxocuprate layers linked by vanadate tetrahedra, of which the sub-layer is formed by joining the zigzag ribbons together in cis zigzag way. Thermogravimetric analysis (TGA) suggests that the structure of compound 1 is quite stable in the temperature range 40−440 °C. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

Two new complexes with three-dimensional extended frameworks linked by pyrazine and malonate ligands, namely [Cu₂(C₃H₂O₄)₂(C₄H₄N₂)]·2H₂O and [Zn₂(OH₂)₂(C₃H₂O₄)₂(C₄H₄N₂)], have been prepared and characterized by X-ray crystallography, IR, EPR and UV/Vis spectroscopy, their magnetic properties and electrical conductivity. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

Since two interesting inorganic “host-guest” polyoxomolybdates 1 and 2 have been reported previously, we have now succeeded in selectively isolating three new acetated “host-guest” polyoxomolybdates 3–5, which considerably extend the range of structures in the cyclic polyoxomolybdate catalogue. 3 crystallizes in the triclinic space group P-1 with a = 1.22235(1) nm, b = 1.52977(2) nm, c = 1.54022(1) nm, a = 113.746(1)°, β = 96.742(1)°, γ = 101.564(1)°, V = 2.51892(4) nm³, Z =1, D_c = 2.568 g. cm⁻³. 4 and 5 crystallize in the monoclinic system: P2(1)/n, a = 1.08298(2) nm, b = 1.54029(1) nm, c = 2.78893(5) nm, β =94.2730(10)°, V = 4.63929(12) nm³, Z = 2 and D_c = 2.671 g. cm⁻³ for 4, and C2/c, a =2.59907(8) nm, b = 1.65992(3) nm, c = 2.28473(7) nm, β-93.4370(10)°, V = 9.8392(5) nm³, Z = 4 and D_c = 2.556 g. cm⁻³ for 5. The structures of 3, 4 and 5 consist of 18-membered “host-guest” polyoxoanions [ Na (X)₂| ∈ |(μ_3-OH)₄Mo^y₈Mo^VI₁₀52(μ₂-CH₃COO)₂]^−(R+9 (X = CH₃COO⁻for 3, DMF for 4 and H₂O for 5), which are connected via Na* ions or hydrogen bonds into infinite extended frameworks.

Two new oxovanadium(V) complexes, [2-MePyH][V^vO₂(L)] (3) and[2-EtPyH][V^vO₂,(L)] (4) (salicylaldehyde 5-bromo salicyloylhydrazone is abbreviated as H₂L; 2-MePyH is protonated 2-Mepyridine; 2-EtPyH presents protonated 2-Et-pyridine) were obtained from a reaction of VOSO₄ and H₂L in acetonitrile-methanol with small quantity of 2-Me-pyridine or 2-Et-pyridine, and characterized by X-ray diffraction and spectroscopic methods. Crystal data: [2-MePyH][VO₂(L)] (3), C₂₀H₁₇N₃O₅BrV, M_r = 510.2, monoclinic, P2₁/n, a = 0.7363(1) nm, 6 = 0.9514(1) nm, c = 2.8594(2) nm, β = 95.305(2)°, Z = 4 and V=1.9946(3) nm³, μ(Mo Kα) = 2.539 mm⁻¹; [2-EtPyH][VO₂(L)] (4), C₂₁H₁₉N₃ O₃BrV, M_r = 524.2, triclinic, P1, a = 0.8051(1) nm, b = 0.9413(1) nm, c = 1.4648(2) nm, α=99.1900(10)°, α = 99.4530(10)°, γ = 104.6670(10)°, Z = 2 and V= 1.0355(2) nm³, μ(Mo Kα) = 2.448 mm⁻¹, X-Ray analyses revealed that the crystal structures of 3 and 4 have similar packing modes.

The open framework of [Eu₂(btc)(H₂btc)(H₂O)]·4H₂O (1), prepared by hydrothermal reaction of EuCl₃ with 1,2,4,5-benzenetetracarboxylic anhydride in acidified aqueous solution, is built up from two types of polymeric layers with [EuO₆(H₂O)]_n units as tethers, resulting in nanoporous channels that host water molecules through complex hydrogen bonding. Crystallographic data for 1: monoclinic, P2₁/n, with a = 10.7562(2) Å, b = 7.2075(2) Å, c = 17.2180(5) Å, β = 97.072(2)° and Z = 2. A study of the temperature dependence of the magnetic susceptibility data reveals that the paramagnetic behavior of 1 is mainly due to the effective spin-orbital coupling between the ground and exited states through the Zeeman perturbation; the magnetic interaction between europium(III) centers is very weak. A study of the electronic properties demonstrates that compound 1 is a semiconductor. A TGA analysis between 30 and 600 °C for 1 suggests that when the lattice water molecules are removed from the network, the skeleton of the network still remains stable up to 150 °C; this is also confirmed by XRPD. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

The reaction of Na₂MoO₄⋅2 H₂O with mercaptoacetic acid and NH₄Cl in H₂O yielded a new complex, (NH₄)₂[Mo₂O₂(μ-SCH₂COO)₂(SCH₂COO)₂] (1). Complex 1 exhibits a bi-octahedral geometry similar to that reported for (Bu₄N)₂[Mo₂O₂(SCH₂COO)₄], but the former is connected via SS interactions to a chain, and then linked to a three-dimensional framework via H-bonds with d(N⋅⋅⋅O)=2.791–2.887 Å and <(NH⋅⋅⋅O) =147–166°. Using a similar reaction system but, additionally, adding the strong reducing reagent NH₂NH₂⋅2 HCl, we have now succeeded in isolating a novel tetranuclear mixed-valence complex (NH₄)Na₃[Mo₄O₂(μ-SCH₂COO)₆(SCH₂COO)₂]⋅10 H₂O (2), representing the first example of a new class of tetranuclear MoS complexes with a linear metalmetal chain. The ⁹⁵Mo-NMR spectrum of 2 exhibits two single peaks at δ 1722.9 and 942.7, attributed to Mo^V and Mo^III, respectively. ¹³C- and ¹H-NMR and magnetic studies are discussed in detail. Crystallographic data of 1: monoclinic space group P2(1)/n, a=11.7595(4), b=5.8320(10), c=13.9728 Å, β=96.587(2)°, V=951.95(5) ų, Z=2, R=0.0378, and g.o.f.=1.106; data of 2: triclinic space group P(−1), a=12.7873(2), b=14.05640(10), c=15.0112(2) Å, α=109.4710(10), β=110.6020(10), γ=101.6020(10)°, V=2220.79(5) ų, Z=2, R=0.0400, and g.o.f.=1.064.