Dongrong Xiao

A series of new polyoxoanion-based inorganic-organic hybrids: (C6NO2H5)[(H2O)4(C6NO2H5)Ln(CrMo6H6O24)]·4H2O (Ln = Ce, Pr, La and Nd) with a chiral layer structure

Four new polyoxoanion-based hybrids with a chiral layer structure, (C6NO2H5)[(H2O)4(C6NO2H5)Ln(CrMo6H6O24)]·4H2O (Ln = Ce, 1; Pr, 2; La, 3 and Nd, 4), have been synthesized and characterized by elemental analysis, IR spectroscopy, TG analysis and single crystal X-ray diffraction. All the compounds are isostructural and crystallize in the monoclinic space group C2/c. Their crystal structures consist of two kinds of chiral layers, one left-handed and the other right-handed, each built up from the same-handed rare earth polyoxometalate helical chains, which leads to mesomeric solid state compounds. To our knowledge, this represents the first example of a 2D chiral layer framework consisting of rare earth polyoxometalate helical chains and organic bridging ligands. The magnetic properties of compounds 1, 2 and 4 have been studied by measuring their magnetic susceptibility over the temperature range of 2–300 K.

Synthesis of novel copper compounds containing isonicotinic acid and/or 2,6-pyridinedicarboxylic acid: third-order nonlinear optical properties

Two novel compounds, [Cu2(pydc)2(inta)2(H2O)2]·3H2O 1 (pydc = 2,6-pyridinedicarboxylic acid, inta =  isonicotinic acid) and [Cu(pydc)2][Cu(H2O)5]·2H2O 2, have been synthesized in aqueous solution and characterized by single-crystal X-ray diffraction, elemental analyses and IR spectra. Compound 1 exhibits reverse saturable absorption and self-defocusing. X-ray structural analysis reveals that Compounds 1 and 2 both possess π–π stacking and hydrogen-bonding interactions forming three-dimensional (3D) networks. Crystal data for 1: a = 7.2345(14), b = 12.219(2), c = 17.069(3) Å, α = 90.44(3), β = 91.82(3), γ = 93.56(3)°, Z = 1, R1 = 0.0435, wR2 = 0.1216. Crystal data for 2: a = 8.3708(17), b = 27.386(6), c = 9.6170(19) Å, α = 90.00, β = 98.14(3), γ = 90.00°, Z = 3, R1 = 0.0742, wR2 = 0.2160.

Hydrothermal synthesis and structures of organic–inorganic hybrid solids based on arsenic-vanadate building blocks

Four novel organic–inorganic hybrid arsenic-vanadate complexes, [Cu(phen)][(AsVO4)(VV 3O7)(H2O)] (1), [Cu(en)2]2[As8V14O42(H2O)] · 2.5H2O (2), [M(1,10-phen)3]2[As8V14O42(H2O)0.5] · 0.5H2O (M = Mn, 3, Cd, 4) (1,10-phen = 1,10-phenanthroline) have been hydrothermally synthesized for the first time and characterized by elemental analyses, XPS spectra, EPR spectra, IR spectra, TG analyses and single crystal X-ray diffraction. The structure of compound 1 consists of arsenic vanadate ribbons coordinated by the [Cu(phen)]2+ complex, while compounds 2 to 4 possess a spherical [As8 IIIV14 IVO42]4− cage with H2O molecules encapsulated. The unexpected preparation 1 and the synthesis of compounds 2 to 4 on the basis of same polyoxoanion structures show that the pH value of the reaction plays a crucial role in controlling the basic architectures.

Structural effects of lone-pair electrons: a novel three-dimensional, open-framework metal selenite constructed from {CoSeO3}n double helical chains linked via ethylenediamine pillars

A novel three-dimensional, open-framework selenite [H2N(CH2)2NH2]0.5·CoSeO3 (1) has been hydrothermally synthesized and characterized by elemental analyses, IR spectrum, XPS spectrum, TG analysis and single crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic system, space group P21/n, with a = 6.6018(14) Å, b = 9.2559(19) Å, c = 7.9097(16) Å, β = 113.56(3)°, V = 443.02(16) Å3, and Z = 4. Compound 1 exhibits an interesting three-dimensional open-framework structure constructed from unique {CoSeO3}n layers aggregated from double helical chains pillared by en ligands. Furthermore, the open framework of 1 possesses three types of one-dimensional channels, in which the triangular channel is particularly rare in covalently bonded microporous materials.

A three-dimensional supramolecular framework built from two-dimensional wave-shaped layers

A new metal-organic coordination polymer, [Fe(4,4′-bpy)(PT)(H2O)2]·2H2O (1) (4,4′-bpy = 4,4′-bipyridine, H2PT = phthalic acid), was prepared by hydrothermal reaction of FeSO4·7H2O, 4,4′-bpy and H2PT at 110°C and characterized by single-crystal X-ray diffraction analysis. The two-dimensional wave-shaped layers are stacked in ABAB sequence, and therefore form a three-dimensional supramolecular architecture. Six-membered rings with the ‘chair’ conformation, formed via hydrogen-bonds, exist between the layers, are symmetrical with respect to the two-fold axes running along b.

Hydrothermal synthesis and characterization of a novel polyoxometallate-templated three-dimensional supramolecular network

The well-known polyoxomolybdate anion [Mo8O26]4− has been used as a noncoordinating anionic template for the construction of a novel three-dimensional (3D) supramolecular network, [Co(phen)3]2[Mo8O26]· 2.5H2O (1) (phen = o-phenanthroline). Compound 1 has been characterized by elemental analyses, IR spectrum, X-ray photoelectron spectroscopy (XPS), TG analysis and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analysis reveals that [Co(phen)3]2+ coordination complexes are packed together via aromatic π–π stacking and hydrogen-bonding interactions, and exhibit an interesting 3D supramolecular network with one-dimensional (1D) box-like channels in which the octamolybdate anions reside.

Synthesis and structure of a novel one-dimensional vanadate constructed from tetravanadate clusters linked via copper–organic complex moieties: [{Cu(phen)(H2O)}2V4O12]

A novel organic–inorganic hybrid copper vanadate [{Cu(phen)(H2O)}2V4O12] (1) (phen = 1,10-phenanthroline) was synthesized by the hydrothermal reaction of V2O5, CuCl2 · 2H2O, phen and water. Complex 1 was characterized by elemental analyses, XPS spectrum, TG analysis, IR spectrum and single-crystal X-ray diffraction. Compound 1 crystallizes in the triclinic system, space group P , a = 7.7715(16) Å, b = 9.3157(19) Å, c = 10.887(2) Å, α = 89.35(3)°, β = 69.63(3)°, γ = 76.41(3)°, V = 716.1(3) Å3, Z = 2, λ(Mo-Kα) = 0.71073 Å, and R(F) = 0.0648. The title compound contains a novel double-chain ribbon constructed from tetravanadate clusters linked through copper–organic complex fragments. To the best of our knowledge, compound 1 represents the first example of one-dimensional vanadium oxide complexes constructed from tetranuclear clusters linked via metal–organic complex moieties.