Xiu-Yan Dong

An unexpected dinuclear Cu(II) complex with a bis(Salamo) chelating ligand: synthesis, crystal structure, and photophysical properties

Abstract An unexpected dinuclear Cu(II) complex, [Cu2(L2)2], has been synthesized via complexation of Cu(II) acetate monohydrate with a bis(Salamo) ligand H2L1. Catalysis of Cu(II) ions results in unexpected cleavage of two N–O bonds in H2L1, giving a dialkoxo-bridged dinuclear Cu(II) complex. Each Cu(II) complex possesses a Cu–O–Cu–O four-membered ring instead of the usual bis(Salamo) [Cu2L1] complex with H2L1. The H2L1 molecule is stabilized by intramolecular O1–H1⋯N1 hydrogen bonds and π⋯π stacking interactions linking adjacent molecules into a 1-D infinite zigzag chain. In the structure of the Cu(II) complex, intermolecular hydrogen bonds have stabilized the Cu(II) complex to form a self-assembling infinite 1-D linear chain. Furthermore, the H2L1 ligand shows intense photoluminescence with two emissions at ca. 370 and 464 nm upon excitation at 310 nm. The Cu(II) complex shows photoluminescence with maximum emission at ca. 423 nm upon excitation at 370 nm.

Synthesis, Characterization, and Crystal Structure of a New Supramolecular CdII Complex With Halogen-Substituted Salen-Type Bisoxime

A new mononuclear CdII complex, [CdL(H2O)2], with halogen-substituted Salen-type bisoxime ligand (H2L = 4,4′-dibromo- 6,6′-dichloro-2,2′-[ethylenedioxybis(nitrilomethylidyne)]diphenol), was synthesized and structurally characterized. The CdII complex crystallizes in the monoclinic system, space group C2/c. The CdII center exhibits a slightly distorted octahedral geometry with halogen-substituted Salen-type bisoxime ligand forming the basal N2O2 coordination plane and two oxygen atoms from the coordinated water molecules in the axial position. An infinite 1D metal-water chain is formed by intermolecular hydrogen-bonding and π-π stacking interactions of neighboring benzene rings. Supplemental materials are available for this article. Go to the publishers online edition of Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry to view the supplemental file.

Synthesis, Characterization, and Crystal Structure of a Supramolecular CoII Complex Containing Salen-Type Bisoxime

A supramolecular CoII complex, [CoL(H2O)2], bearing Salen-type bisoxime chelate ligand 4,4′,6,6′-tetrachloro-2,2′-[ethylenedioxybis(nitrilomethylidyne)]diphenol (H2L), has been synthesized and structurally characterized by elemental analyses, IR spectra, UV–vis spectra, and X-ray diffraction techniques. The crystal structure of [CoL(H2O)2] indicates that the CoII complex consists of one CoII atom, one L2– unit, and two coordinated water molecules. The CoII complex exhibits slightly distorted octahedral geometry with the Salen-type bisoxime ligand forming the basal N2O2 coordination plane and two oxygen atoms from the coordinated water molecules in the axial positions. An infinite 1D metal–water chain and 2D supramolecular network structure were formed by intermolecular O-H···O, O-H···Cl, and C-H···O hydrogen bonding and π-π stacking interactions. Supplemental materials are available for this article. Go to the publishers online edition of Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry to view the supplemental file.

A 2D Supramolecular Copper(II) Complex With an Asymmetric Salamo-Type Ligand: Synthesis, Crystal Structure, and Fluorescent Property

A new Cu(II) complex with asymmetric Salamo-type ligand (H2L, 4-bromo-6′-ethoxy-2,2′-[ethylenedioxybis(nitrilomethylidyne)]diphenol) has been synthesized and characterized structurally. The X-ray crystal structure of the Cu(II) complex shows it to be a binuclear complex, in which each Cu(II) atom is in a distorted square-pyramidal geometry. The Cu(II) complex crystallizes in the monoclinic system, space group P21/c, with unit cell parameters a = 14.7109(1), b = 8.6254(7), c = 30.124(3) Å, β = 100.7400(1), and Z = 4. The Cu(II) complex consists of two Cu(II) atoms, and two L2– units, and each Cu(II) complex molecule links four other molecules into an infinite 2D-layer supramolecular structure. Meanwhile, the Cu(II) complex exhibits emission with the maximum emission wavelength λmax = 443 nm when excited at λex = 340 nm.

A tetradentate bisoxime and its supramolecular nickel(II) cluster: synthesis, crystal structure, and spectral properties

Salen-type bisoxime 5,5′-dimethoxy-2,2′-[(ethylenedioxy)bis(nitrilomethylidyne)]diphenol (H2L) and its trinuclear Ni(II) cluster {[(NiL)(n-BuOH)]2(μ-OAc)2Ni} · n-BuOH have been synthesized and structurally characterized. The structure of H2L adopts an L-shape conformation where the two salicylaldoxime moieties are well separated. In the trinuclear Ni(II) cluster, two acetates coordinate to three Ni(II)s through Ni–O–C–O–Ni bridges, four μ-phenoxos from two [NiL(n-BuOH)] units also coordinate to Ni(II), and two n-butanols coordinate to two terminal Ni(II)s forming a distorted octahedral geometry. The Ni–O–C–O–Ni and μ-phenoxo bridges play important roles in assembling Ni(II) and the ligands. H2L forms a rectangle-like large cave structure through O–H ··· N, C–H ··· O, and C–H ··· π hydrogen-bond interactions, whereas its trinuclear Ni(II) cluster exhibits a 3-D supramolecular network structure through intermolecular O–H ··· O, C–H ··· O, and C–H ··· π hydrogen-bond interactions.

Zinc(II) and copper(II) complexes containing asymmetrical Salamo-type ligands: syntheses, crystal structures, and spectroscopic behaviors

[Zn4(L1)2(OAc)2(CH3CH2OH)2] and [CuL2(H2O)] with new asymmetric Salamo-type ligands have been synthesized and characterized. There are two coordination geometries (trigonal bipyramidal and square pyramidal) in the Zn(ΙΙ) complex, and the Cu(II) complex has square-pyramidal geometry. A self-assembling continual zigzag chain is formed by intermolecular hydrogen bonds in the Cu(II) complex. The self-assembling array of the Zn(II) complex is linked by intermolecular C–H⋯O and C–H⋯π interactions. Blue emissions of the Zn(II) and Cu(II) complexes in DMF solution are exhibited by fluorescence.

Synthesis, crystal structure, luminescence and electrochemical properties of a Salamo-type trinuclear cobalt(II) complex

Abstract A trinuclear Co(II) complex, [{CoL(C4H9OH)}2-(OAc)2Co]·C3H7NO, was synthesized by the reaction of a Salamo-type chelating ligand (H2L=4,42′-dinitro-2,2′-[1,2-ethylenedioxybis(nitrilomethylidyne)]diphenol) with cobalt(II) acetate tetrahydrate in n-butanol, and characterized by elemental analyses, X-ray crystallography, FT-IR and UV/Vis spectra. In the Co(II) complex, there are two ligand L2− units, two μ2-acetate ions, two coordinated n-butanol molecules and one non-coordinated N,N-dimethylformamide molecule. The Co(II) atoms in the structure of the Co(II) complex adopt slightly distorted octahedra geometries. Furthermore, through intermolecular C–H···O, O–H···O and C–H···π interactions, infinite layer-like, plane-like and 3D supramolecular structures are constructed. The fluorescence and electrochemical properties of the Co(II) complex have also been investigated.

A Dinuclear Copper(II) Complex Based On the Bisoxime Ligand 5,5 -Dimethoxy-2,2 -((ethylene)dioxybis(nitrilomethylidyne))diphenol: Synthesis, Crystal Structure and Spectral Properties

A dinuclear Cu(II) complex, [Cu2(L2)2] (H2L2 = 4-methoxysalicylaldehyde O-(2-hydroxyethyl)- oxime), has been synthesized through the complexation of Cu(II) acetate monohydrate with the ligand H2L1 (H2L1 = 5,5´ -dimethoxy-2,2´-[(ethylene)dioxybis(nitrilomethylidyne)]diphenol), and characterized by elemental analyses, IR, UV/Vis and emission spectra. The crystal structure of the Cu(II) complex has been determined by single-crystal X-ray diffraction. The catalysis by Cu(II) ions results in the unexpected cleavage of the N-O bonds in the ligand H2L1, giving a novel dialkoxo-bridged dinuclear Cu(II) complex possessing a Cu-O-Cu-O four-membered ring core instead of the expected salen-type bisoxime Cu-N2O2 complex Graphical Abstract A Dinuclear Copper(II) Complex Based On the Bisoxime Ligand 5,5´-Dimethoxy-2,2´-[(ethylene)dioxybis(nitrilomethylidyne)]diphenol: Synthesis, Crystal Structure and Spectral Properties

Bis{(E)-2-[1-(eth-oxy-imino)-eth-yl]-1-naphtho-lato-κN,O}copper(II).

In the title complex, [Cu(C14H14NO2)2], the discrete complex molecules have crystallographic inversion symmetry. The slightly distorted square-planar coordination sphere of the CuII atom comprises two phenolate O atoms and two oxime N atoms from two bidentate–chelate 2-[1-(ethoxyimino)ethyl]-1-naphtholate O-ethyl oxime (L −) ligands [Cu—O = 1.8919 (17) Å and Cu—N = 1.988 (2) Å]. The two naphthalene ring systems in the molecule are parallel, with a perpendicular interplanar spacing of 1.473 (2) Å, while each complex unit forms links to four other molecules via intermolecular methyl C—H⋯π interactions, giving an infinite cross-linked layered supramolecular structure