Cyano-bridged pentanuclear and honeycomblike M(III)Cu(II) (M = Fe, Cr) bimetallic assemblies: structural variations modulated by side groups of macrocyclic ligands and magnetic properties.

Three two-dimensional (2D) layered M(III)-Cu(II) (M = Fe, Cr) bimetallic complexes and a discrete cluster were prepared using [M(CN)(6)](3-) and respective Cu macrocycles with methyl (1, 3) or ethyl (2, 4) side groups. The crystal structures can be described as aesthetic honeycomb-like M(2)Cu(3) neutral sheets (1, 3, 4) and a pentanuclear Fe(2)Cu(3) entity (2) with an isolated Cu(L2)(2+) moiety. The steric hindrance induced by the pendant groups renders the internal parameters of the Cu-N(ax) (where the "ax" subscript denotes axial) length and Cu-N(ax)-C(ax) angle to become elongated and acute.

Bimetallic M(V)(2)Cu(II)(3) (M = Mo, W) coordination complexes based on octacyanometalates: structures and magnetic variations tuned by chelated tetradentate macrocyclic ligands.

Four octacyanometalate-based bimetallic Cu-M (M = Mo, W) assemblies coordinated by tetradentate macrocyclic ligands were prepared via self-assembly process in a stoichiometric ratio of [M(CN)8]3- and Cu(macrocycle)2+ and characterized in terms of structures and magnetic properties. The crystal structures are varied depending on the macrocycles used. The employment of cyclam with no pendant groups produced a one-dimensional chain (1) with a rope-ladder pattern, whereas macrocycles with side groups allowed for the formation of two-dimensional honeycomb-like architectures (2-4).

Two WV-MnIII bimetallic assemblies built by octacyanotungstate(v) and MnIII Schiff bases: molecular structures and a spin-flop transition.

Two W(V)-Mn(III) bimetallic compounds, [Mn(Cl-salmen)(H(2)O)2]{[Mn(5-Clsalmen)(H(2)O)]2[W(CN)8].2H(2)O (1.2H(2)O) [5-Clsalmen = N,N'-(1-methylethylene)bis(5-chlorosalicylideneiminato) dianion], which contains trinuclear Mn(2)W and isolated Mn(III) moieties, and [Mn(3-MeOsalcy)(H(2)O)2]3[W(CN)(8)].

Cyanide-bridged W(V)-Co(II) double-zigzag chain based on an octacoordinated W precursor: metamagnetism and spin canting.

A cyanide-bridged W-Co bimetallic complex (1) with a double-zigzag chain structure was characterized in terms of structure and magnetism. Compound 1 exhibits metamagnetism and spin canting induced by the presence of anisotropic CoII ions and noncovalent interactions.

Cyanide-bridged single-molecule magnet constructed by an octacoordinated [W(CN)6(bpy)]- anion.

Two cyanide-bridged WV-M [M = Mn(II) (1), Co(II) (2)] bimetallic clusters were prepared by self-assembling a new molecular precursor [W(CN)6(bpy)]- and the corresponding metal complexes. Compound 1 shows a tetranuclear W2Mn2 entity, consisting of a Jahn-Teller ion, Mn(III), which serves as an anisotropic source, while compound 2 exhibits a trimeric W2Co structure. Among them, compound 1 displays slow relaxation of the magnetization, which is typical of a single-molecule magnet behavior.

Coexistence of spin canting and metamagnetism in a one-dimensional Mn(III) complex bridged by a single end-to-end azide.

Two manganese(III) azide complexes capped with tetradentate Schiff bases were characterized structurally and magnetically. The replacement of halogens on the Schiff bases leads to a drastic structural alteration from a dimer (1) bridged by phenoxide to a one-dimensional chain (2) linked by azide in a single end-to-end mode. Notably, magnetic studies of 2 show the concomitant existence of spin canting and metamagnetism.

Synthesis, crystal structures, and magnetic properties of cyano-bridged honeycomblike layers M(V)-Cu(II) (M = Mo, W) chelated by a macrocyclic ligand.

Two cyano-bridged Cu(II)-M(V) [M = Mo (2), W (3)] complexes formed by self-assembly of octacyanometalates [M(CN)8]3- (M = Mo, W) with a new molecular precursor [Cu(L2)]2+ (1) (L2 = a macrocyclic ligand) in a 2:3 ratio have been investigated in terms of structures and magnetic behaviors. The M2Cu3 repeating unit of both bimetallic compounds is extended to a two-dimensional honeycomblike layered structure. The pendant ethyl groups on L2 noticeably influence the structural parameters around the Cu center.

Methylpyrazole-capped two-dimensional supramolecular M(II) (M = Mn, Ni, Co) assemblies constructed by covalent and noncovalent interactions: uncommon coordination modes of methylpyrazoles and magnetic properties.

Two mononuclear complexes [Mn(5-methylpyrazole)4(N3)2] (1) and [Ni(5-methylpyrazole)4(N3)2] (2), as well as a novel one-dimensional coordination polymer [Co(3-methylpyrazole)2(5-methylpyrazole)2(tp)]n (3) (tp = terephthalate), were characterized. The isostructural complexes, 1 and 2, display two-dimensional supramolecular networks formed by hydrogen bonds between the N-H groups of 5-methylpyrazoles and the end N atoms of the azide ligands and additional face-to-face pi-pi interactions of the 5-methylpyrazoles. For 3, tp-bridged one-dimensional chains assisted by intrachain hydrogen bonds among the N-H groups of methylpyrazoles and carboxylate oxygens are connected with the help of interchain C-H.

Cyano-bridged CuII-MV (M = Mo, W) bimetallic layered complexes exhibiting novel honeycomblike structures.

Self-assembly of a new precursor [Cu(L)](ClO4)2 (1) (L = macrocyclic ligand) with octacyanometalates [M(CN)8]3- (M = Mo, W) produced two-dimensional cyano-bridged Cu(II)-M(V) bimetallic assemblies [Cu(L)]3n[M(CN)8]2n.6nH2O [M = Mo (2), W (3)] with novel honeycomblike structures, characterized by spectroscopic data, single-crystal X-ray diffraction studies, and magnetic measurements. The crystallographic determination reveals that compounds 2 and 3 are isostructural and crystallize in the triclinic system (P).