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Heterotrinuclear 3d–4f complexes with a naphthalenediol-based acyclic bis(salamo)-type ligand have been synthesized and structurally characterized. Spectral titrations clearly show that the heterotrinuclear complexes [Zn 2 (L)La(OAc) 3 ] ( 1 ), [Zn 2 (L)Ce(OAc) 3 ] ( 2 ) and [Zn 2 (L)Dy(OAc) 3 (CH 3 OH)]·CH 2 Cl 2 ( 3 ) are acquired by the substitution reaction of the obtained homotrinuclear Zn(II) complex with 1 equiv. of Ln(NO 3 ) 3 (Ln 3 + = La 3 + , Ce 3 + and Dy 3 + ). Two Zn(II) ions are penta- and hexa-coordinated with geometries of distorted tetragonal pyramid and octahedron. La(III) ion is deca-coordinated, adopting a distorted bicapped square antiprism geometry. Ce(III) ion is nona-coordinated with geometry of distorted capped square antiprism as well as Dy(III) ion. The different coordination modes of acetate ions in complexes 1 , 2 and 3 lead to different coordination numbers of the lanthanide(III) ions. Furthermore, the structures and fluorescence properties have been discussed. [ABSTRACT FROM AUTHOR]

Highlights: [•] A halogen-substituted Salen-type bisoxime has been synthesized firstly. [•] A new complex [ZnL(H2O)2] n has been synthesized and characterized structurally. [•] The complex forms a self-assembling infinite dual metal–water chain-like structure. [•] Some new results are very important to coordination and supramolecular chemistry. [Copyright &y& Elsevier]

Abstract: Mononuclear and trinuclear Cu(II) complexes with chemical formula [CuL]·CH3OH (1) and [{(Cu(μ-L))2(OAc)2}Cu] (2), where H2L=2,2′-[1,1′-(ethylenedioxydinitrilo)diethylidyne]diphenol, have been synthesized and characterized by elemental analyses, 1H NMR, IR and UV–vis spectra et al. Crystallographic data of complex 1 reveal the formation of an asymmetric mononuclear structure and a slight distortion toward tetrahedral geometry from the square planar structure, in which the introduction of the non-coordinated methanol molecule lead to the assembly of the 1D chains by hydrogen bonding, Cu⋯π and π⋯π interactions. Complex 2 have the elongated square pyramidal geometries for the two terminal Cu(II) ions and an octahedral coordinated geometry for the central Cu(II) ion. In complex 2, two acetate ions coordinate to three Cu(II) ions adopting a familiar syn–syn (μM-O-C-O-M) coordinated fashion. The central Cu(II) ion sits in a crystallographic inversion centre. Therefore, the whole molecule of complex 2 is rigorously centrosymmetric, and forms a 3D supramolecular networks through intermolecular C–H⋯O and C–H⋯π interactions. [Copyright &y& Elsevier]

Abstract: Two solvent-induced trinuclear nickel(II) clusters, [{NiL(CH3OH)}2(OAc)2Ni]·2CH3OH (I) and [{NiL(C2H5OH)}2(OAc)2Ni]·2C2H5OH (II), have been synthesized by the reaction of a new Salen-type bisoxime chelating ligand of 5,5′-di(N,N′-diethylamino)-2,2′-[(1,3-propylene)dioxybis(nitrilomethylidyne)]diphenol (H2L) with nickel(II) acetate tetrahydrate in different solvents. Clusters I and II were characterized by elemental analyses, IR spectra, UV–vis absorption spectra, TG–DTA and X-ray diffraction methods. In clusters I (or II), there are two ligand moieties (which provide N2O2 donors), two acetate ions, two coordinated methanol (or ethanol) molecules and two crystallizing methanol (or ethanol) molecules, which result in the formation of three slightly distorted octahedral geometries around Ni(II) ions. Interestingly, nickel(II) ions in the structures of clusters I and II are all six-coordinated geometry, but clusters I and II are grown up in different solvent. Right because of this, solvent effect cause to their different crystal structures. [Copyright &y& Elsevier]

Four novel butterfly-shaped hetero-pentanuclear 3d–4f complexes [Zn 4 (L) 2 Sm(H 2 O) 4 ]3NO 3 ·2EtOH ( 1 ) [Zn 4 (L) 2 Eu(NO 3 ) 2 (MeOH)(EtOH)]NO 3 ·H 2 O ( 2 ), [Zn 4 (L) 2 Gd(H 2 O) 4 ]3NO 3 ·MeOH·EtOH ( 3 ) and [Zn 4 (L) 2 Tb(NO 3 )(EtOH)(H 2 O) 2 ]NO 3 ·MeOH·EtOH ( 4 ) were synthesized by the reactions of a bis(salamo)-type tetraoxime ligand (H 4 L) with Zn(OAc) 2 ·2H 2 O and Ln(NO 3 ) 3 ·6H 2 O (Ln = Sm, Eu, Gd and Tb), respectively. The structures of complexes 1 – 4 were fully characterized by elemental analyses, FT–IR, UV–Vis spectroscopy and single crystal X-ray crystallography, and their luminescence properties were also discussed. In addition, cyclic voltammograms were used to characterize electrochemical properties of the Zn(II)–Ln(III) (Ln = Sm, Eu, Gd and Tb) complexes. [ABSTRACT FROM AUTHOR]

wo unusual Cu(II) complexes [{Cu(L 1 )} 2 ] (1) and [Cu 2 (L 2 )] (2), with an asymmetric salamo-type bisoxime ligand H 2 L 1 were synthesized and characterized by elemental analyses, UV–Vis, fluorescent spectra, Hirshfeld surface analyses and single-crystal X-ray diffraction analyses. For the complex 1 , two Cu(II) ions are penta-coordinate by N 2 O 2 donor atoms from the (L 1 ) 2− unit and one bridged phenol oxygen atom from another (L 1 ) 2− unit. Complex 1 does not have intermolecular hydrogen bonds, formed an isolated zero dimensional structure. Meanwhile, for the complex 2 , an unexpected ligand H 4 L 2 was synthesized by aldol condensation reaction of H 2 L 1 and acetone upon coordination, then the new ligand and Cu(II) ions combined, formed a highly symmetrical structure, and two Cu(II) ions of the complex 2 have tetra-coordinate environment. With the help of intermolecular hydrogen bonding C H⋯O interactions, a self-assembled infinite 1D supramolecular structure was formed. Meanwhile, the photophysical spectra and Hirshfeld surface analyses of the complexes 1 and 2 were also measured and discussed. [ABSTRACT FROM AUTHOR]