Ke-Chang Li

Secondary organic moiety templated organic–inorganic polyoxometalate-based frameworks

Four new organic–inorganic hybrid compounds, namely, [Cu3(4,4′-bpy)3][HSiW12O40]·(C3H4N2) (1), [Cu3(4,4′-bpy)3][PMo12O40]·(C5H6N2)·0.5H2O (2), [Cu2(4,4′-bpy)2][HPMo12O40]·(C5H6N2) (3) and [Cu(Phen)(4,4′-bpy)(H2O)]2[PW12O40]·(4,4′-bpy) (4) (C3H4N2 = imidazole, C5H6N2 = 2-aminopyridine, bpy = bipyridine, Phen = 1,10-phenanthroline), have been synthesized and characterized by IR, UV-vis, powder XRD, cyclic voltammetry analysis, photoluminescence analysis, elemental analyses and single crystal X-ray diffraction. The four compounds represent new examples of secondary organic moiety templated frameworks constructed from Keggin polyanions, metal ions and organic ligands. Compounds 1 and 2 present 3-D framework structures; compound 3 exhibits a 1-D ladder-like structure and compound 4 shows a 2-D layered framework structure. It is noted that the packing structures of compounds 1 and 2 are almost identical; however, the crystal space groups and cell parameters of the two are thoroughly different. Such a phenomenon has also been observed between compound 3 and a compound recently reported by us. Compound 4 is the first framework structure constructed from polyoxometalates, metal ions and mixed organic ligands. In addition, all the four frameworks are combined with dissociated organic moieties as templates.

Synthesis, crystal structure and third-order non-linear optical properties of a cobalt(II) one-dimensional supramolecular compound

A cobalt(II) thiocyanate complex [Co(py)4(NCS)2] 1 (py = pyridine) has been synthesized by low-temperature solid-state reaction. Single crystal X-ray analysis reveals that 1 possesses a one-dimensional (1-D) zigzag chain structure. Each Co ion is symmetrically coordinated by four pyridine ligands and also coordinates with two NCS− anions. Compound 1 was characterized by elemental analyses, IR spectra and UV-visible spectra. The third-order non-linear optical (NLO) properties were also investigated and they exhibit non-linear absorption and self-defocusing performance with modulus of the hyperpolarizability 9.46 × 10−30 esu for 1 in a 3.6 × 10−4 mol dm−3 DMF solution.

Synthesis, crystal structure, and third-order nonlinear optical properties of a copper(I) one-dimensional coordination polymer

A copper(I) thiocyanate coordination polymer [Cu(Phen)(μ-NCS)]n (I) (Phen = 1,10-phenan-throline) has been synthesized by the low-temperature solid-state reaction. Single-crystal X-ray analyses reveal that compound I possesses a type of one-dimensional (1D) framework structure. Polymer I was characterized by elemental analyses, IR spectra, and UV-visifele spectra. The third-order nonlinear optical properties were also investigated, and they exhibit good nonlinear absorption and self-defocusing performance with modulus of the hyperpolarizability 4.94 × 10−30 esu for I in a 6.35 × 10−4 mol dm−3 DMF solution.

Synthesis, crystal structure, and third-order non-linear optical properties of a new Cd(II) polymer constructed from pyrazine-2-carboxylic acid

A new cadmium(II) pyrazine-2-carboxylate coordination polymer, {[Cd(L)(H2O)2(SO4)0.5]2·H2O}n (1) (HL = pyrazine-2-carboxylic acid), has been synthesized by low-temperature solid-state reaction. Single-crystal X-ray analyses reveal that 1 possesses a 3-D framework structure. The polymer 1 was characterized by elemental analyses, thermogravimetric analyses, X-ray powder diffraction analyses, IR spectra, and UV–visible spectra. The third-order non-linear optical properties were also investigated and they exhibit nice non-linear absorption and self-defocusing performance with modulus of the hyperpolarizability (γ) 1.30 × 10−30 esu for 1 in a 2.01 × 10−4 M dm−3 DMF solution. Graphical Abstract A new cadmium(II) pyrazine-2-carboxylate coordination polymer, {[Cd(L)(H2O)2(SO4)0.5]2·H2O}n (HL = pyrazine-2-carboxylic acid), has been synthesized by low-temperature solid-state reaction. Single-crystal X-ray analyses reveal that compound possesses a 3-D framework structure. The third-order non-linear optical properties were also investigated and they exhibit nice non-linear absorption and self-defocusing performance with modulus of the hyperpolarizability (γ) 1.30 × 10−30 esu.

Synthesis, crystal structure, and third-order nonlinear optical properties of a copper(I) one-dimensional coordination polymer [Cu(μ-1,1,1,3-N3)]n

A novel copper(I) azide coordination polymer [Cu(μ-1,1,1,3-N3)]n has been synthesized by the low-temperature solution-state reaction. Crystal X-ray analyses reveal that compound [Cu(μ-1,1,1,3-N3)]n possesses a type of three-dimensional (3D) framework structure. The polymer was characterized by elemental analyses, IR spectra, and UV-Vis spectra. The third-order nonlinear optical (NLO) properties were also investigated, and they exhibit good linear absorption and self-defocusing performance with modulus of the hyperpolarizability (γ) 8.16 × 10−30 esu for [Cu(μ-1,1,1,3-N3)]n in a 1.96 × 10−4 mol dm−3 DMF solution.

Synthesis, structure, and third-order nonlinear optical properties of W/S cluster [Fe(DMF)6][W2(μ2-S)2S4]

The homometal cluster [Fe(DMF)6][W2(μ2-S)2S4] (I) was successfully synthesized by low-temperature solid-state reactions. X-ray single-crystal diffraction studies suggest that compound I is a dinuclear anion cluster. The compound was characterized by elemental analyses, IR spectra, and UV-Vis spectra. The third-order nonlinear optical (NLO) properties of the cluster were also investigated and exhibited nice nonlinear saturation absorption (α2 < 0) that is rarer than reverse saturation absorption (α2 > 0) and self-defocusing property (n2 < 0) and self-defocusing performance with modulus of the hyperpolarizabilities (9.547 × 10−31 esu) for I.