Three-dimensional Supramolecular Compound Research Articles

Thermolysis preparation of cadmium(II) oxide nanoparticles from a new three-dimensional cadmium(II) supramolecular compound

The reaction of cadmium(II) chloride and 4-pyridine carboxylic acid (4-Hpyc) produces a new threedimensional supramolecular compound [Cd(4-pyc)2(H2O)4] n (1). Compound 1 is characterized by IR spectroscopy and elemental analyses. The single crystal X-ray data show an infinite three-dimensional structure formed by the hydrogen bonding and π-π stacking interactions. The CdO nanoparticles are obtained by direct calcination at 400°C, 500°C and 600°C in the air atmosphere as well as by thermolysis in oleic acid at 200°C. The obtained cadmium(II) oxide nanoparticles are characterized by X-ray diffraction and scanning electron microscopy. This study demonstrates another potential application of cadmium(II) supramolecular compounds in the preparation of nanoscale cadmium(II) oxide materials with a specific size and morphologies.

A blue-green-emitting 3D supramolecular compound: synthesis, crystal structure and effect of solvents and temperature on the luminescent properties

A blue-green-emitting three-dimensional supramolecular compound (C10O2N2H8)(C9O7H6) (1) was synthesised under hydrothermal conditions and structurally characterised by elemental analysis, IR spectrum, 1H NMR and single-crystal X-ray diffraction. The crystal belongs to triclinic system with P 1¯ space group. The crystal structure is stabilised by O–H…O, O–H…N hydrogen bonds and π–π interactions (π–π stacking distance is 3.282 Å). Compound 1 exhibits intense green luminescence in solid state at 298 K (λem = 546 nm). In addition, absorption and fluorescence characteristics of compound 1 have been investigated in different solvents (DMSO, CH3CN and CH3OH). The results show that compound 1 exhibits a large red shift in both absorption and emission spectra as solvent polarity increases (polarity: DMSO>CH3CN>CH3OH), indicating a change in dipole moment of compound 1 upon excitation. Although the emission spectra of compound 1 in CH3OH are close to it in dimethyl sulfoxide (DMSO), it is revealed that the luminescence behaviour of compound 1 depends not only on the polarity of environment but also on the hydrogen bonding properties of the solvent. Meanwhile, temperature strongly affects the emission spectra of compound 1. Emission peaks of compound 1 were blue shift at 77 K than those at 298 K in both solid state (ca. 142 nm) and solution (ca. 6–23 nm), which was due to the non-radiative transition decreases at low temperature. Moreover, the quantum yield and fluorescence lifetime of compound 1 were also measured, which increased with increasing polarity of solvent, lifetime in DMSO at 298 K (τ1 = 0.92 μs, τ2 = 8.71 μs) was the longest one in solvents (298 K: τ1 = 0.87–0.92 μs, τ2 = 7.50–8.71 μs; 77 K: τ1 = 0.72–0.90 μs, τ2 = 6.88–7.45 μs), which was also shorter than that in solid state (298 K: τ1 = 1.13 μs, τ2 = 7.50 μs; 77 K: τ1 = 0.97 μs, τ2 = 8.97 μs). This was probably because of the weak polarity environment of compound 1 in solid state.

Synthesis, Crystal Structure, and Luminescence of a Three-Dimensional Supramolecular Compound Based on a Dinuclear Tin Cluster

A three-dimensional (3D) supramolecular compound, [(phen)LSnS]2·(H2O)2 (phen = 1,10-phenanthroline, L = mercaptoacetic acid), has been synthesized and the crystal structure was determined by a single crystal X-ray diffraction study. 1 is triclinic, space group P-1 with a = 6.695(1) Å, b = 10.929(2) Å, c = 12.117(2) Å, α = 114.55(3)°, β = 93.53(2)°, γ = 104.06(3)°, and Z = 1. The dinuclear cluster of [(phen)LSnS]2 and H2O are linked into a 3D supramolecular framework by a combination of O‒H…O, C‒H…O hydrogen bonds and π–π stacking interactions. Its luminescence property is discussed.

Synthesis, Characterization and Crystal Structure of a Novel Three-Dimensional Supramolecular Architecture Formed by Cobalt(II) and Pyridine-2,5-dicarboxylic Acid

A novel three-dimensional supramolecular compound formed by Co(II) and pyridine-2,5-dicarboxylic acid of formula [Co(Pydc)2(H2O)2] (1) (Pydc = pyridine-2,5-dicarboxylic acid) has been synthesized and characterized by elemental analyses, IR, UV-vis spectra, thermogravimetric analysis and X-ray diffraction techniques. The complex 1 crystallizes in the Monoclinic crystal system, space group C12/c1 with a = 8.529(3), b = 12.164(4), c = 15.436(6)Å, β = 101.590(6)° and Z = 4. X-ray structural analysis of reveals that the central Co(II) ion is coordinated by two water molecules and two chelated Pydc ligands, and the intermolecular hydrogen bonds play an important role on the additional stabilization to construct the supramolecular networks in the packing structure. The water molecules coordinate with Co(II) ions in a cis mode in the complex 1.

Synthesis, characterization and crystal structure of a novel three-dimensional supramolecular architecture formed by manganese(II) and pyridine-2,5-dicarboxylic acid

A novel three-dimensional supramolecular compound formed by Mn(II) and pyridine-2,5-dicarboxylic acid of formula [Mn(Pydc)2(H2O)2] (Pydc = pyridine-2,5-dicarboxylic acid) has been synthesized and characterized by elemental analyses, IR, electronic spectra, thermogravimetric analysis and X-ray diffraction techniques. The X-ray structure shows that the central Mn(II) ion is coordinated by two water molecules and two chelated Pydc ligands. Water molecules coordinate with Mn(II) ions in the cis mode. Intermolecular hydrogen bonds play an important role in stabilization of the lattice and construction of the supramolecular network.

Fluorescent property of a three-dimensional supramolecular compound assembled through combined weak intermolecular interactions

The three-dimensional supramolecular compound [Cd(phen)(H 2O) 2SO 4] n 1 (phen = 1,10-phenanthroline) has been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction, elemental analysis, IR spectrum, diffuse reflectance UV–vis. This compound displays the self-assembly three-dimensional supramolecular framework. The sulfate μ 2−bridged Cd(II)-phen complex 1 consists of [Cd(H 2O) 2(phen)(SO 4)] chains, which are generated from Cd atoms in distorted octahedral sites interlinked by bidentate sulfate bridges. These chains are held together via interchain hydrogen bonds formed between water and sulfate O atoms to form a two-dimensional layer. Interdigitation of phen ligands leads to the formation of the three-dimensional network stabilized by significant π⋯ π stacking and weak C–H⋯O hydrogen bonds interactions. The fluorescent measurement of 1 has been performed at room temperature in the solid state and DMF solutions and shows strong fluorescent emission. The strong fluorescent emission makes 1 as a potential photoactive material.

Zn(INO) 2(DMF)]·DMF: A new three-dimensional supramolecular open framework containing one-dimensional channels

A three-dimensional supramolecular compound, [Zn(INO) 2(DMF)]·DMF (1) (INO=isonicotinic acid N-oxide), has been prepared in the DMF solution at room temperature, and characterized by elemental analysis, TG and single crystal X-ray diffraction. The three-dimensional supramolecular open framework of 1 contains rectangular channels with the dimensions of 9.02×10.15 Å, assembled from one-dimensional helical chains via hydrogen-bonding and π–π stacking interactions. Furthermore, compound 1 shows blue photoluminescence at room temperature.

Synthesis, structure and non-linear optical property of a copper(II) thiocyanate three-dimensional supramolecular compound

A novel copper(II) thiocyanate complex [Cu(im) 2(NCS) 2] 1 (im=imidazole) has been prepared and characterized by spectroscopic analysis and crystallographic method. This supramolecular compound exhibits a three-dimensional solid state structure constituted by N–H⋯S hydrogen bonds and π–π stacking interactions. The compound in DMF solutions has a very strong third-order non-linear optical (NLO) behavior with absorption coefficient and refractive index α 2=1.18×10 −11 m w −1, n 2=−9.00×10 −16 m 2 w −1, respectively, and third-order NLO susceptibility χ (3) of 7.00×10 −10 esu.

Hydrothermal synthesis, crystal structure and third-order non-linear optical property of a novel three-dimensional supramolecular network compound [Ni(IN) 2(H 2O) 4] (IN=isonicotinate)

A three-dimensional supramolecular compound [Ni(IN) 2(H 2O) 4] 1 has been rationally designed and synthesized by hydrothermal method, and the structure was characterized with elemental analysis, FT–IR spectrum and X-ray diffractometer. In the packing structure, the stronger intermolecular O–H⋯O hydrogen-bonded and π–π stacking interactions are the most significant factors of controlling the novel supramolecular sheet fashion for the title compound. The third-order non-linear optical property of compound 1 was also investigated, and it exhibits nicer reverse saturable absorption and self-focusing performance.

A New Azide-Bridged Three-Dimensional Supramolecular Manganese(II) Compound: Synthesis, Crystal Structure and Magnetic Properties

A three-dimensional supramolecular compound [Mn(N3)2(H2O)3(hmt)] 2 , where hmt stands for hexamethylenetetramine, was synthesized and characterized by IR, crystal structure and magnetic susceptibility. The compound [Mn(N3)2(H2O)3(hmt)] n , crystallizes in the orthorhombic system, space group Pn 21 a, with a = 6.5201(9), b = 9.322(2), c = 22.192(3) Å, β = 90° and Z = 2. The Mn atom is coordinated in an octahedral arrangement by three nitrogen atoms from three azido ions, and three oxygen atoms from three water molecules, respectively. The azide ligand bridges Mn atoms in μ-1,3 fashion, forming a zigzag chain. Hmt connected with the zigzag chain by hydrogen bonds, to form a three-dimensional supramolecular structure. The magnetic susceptibility data show that there is an antiferromagnetic exchange interaction in the title compound. The data were modeled using an infinite chain model leading to J = -4.8 cm−1.