Cyano-bridged 2D Cu(II)-Cr(III) coordination polymers: structural evidence for formation of a polymeric macrocyclic metallic compound.

Two unique cyano-bridged 2D coordination polymers have been synthesized and characterized structurally and magnetically. The complexes contain two polyaza Cu(II) units and one novel macromolecular Cu(II) moiety, which have been synthesized via one-pot metal template condensation reactions involving ethylenediamine (en) and formaldehyde. Self-assembly of the polyaza Cu(II) mixture with [Cr(CN)(6)](3)(-) gave rise to two layered complexes. One complex contains unprecedented covalently linked polymeric Cu(II) chains and cyano-bridged Cu(II)(-)Cr(III) coordination chains, which are interwoven to form a novel layer. The other complex shows intriguing encapsulation of [Cr(CN)(6)](3)(-) anions. Intermetallic ferromagnetic coupling is operative within the bridged 2D layer. The magnetic susceptibilities of both complexes were simulated using approximate models.

Heterotrimetallic 4f-3d coordination polymers: synthesis, crystal structure, and magnetic properties.

A series of cyano-bridged heterotrimetallic complexes [CuL](2)Ln(H(2)O)(2)M(CN)(6).7H(2)O have been synthesized by the reactions of CuL (L(2)(-) = dianion of 1,4,8,11-tetraazacyclotradecane-2,3-dione), Ln(3+) (Ln = Gd or La), and [M(CN)(6)](3)(-) (M = Co, Fe, or Cr). X-ray diffraction analysis reveals that these complexes are isostructural and have a novel chain structure. The Ln(3+) ion is eight-coordinated by six oxygen atoms of two CuL and two water molecules and two nitrogen atoms of the bridging cyano ligands of two [M(CN)(6)](3)(-), while the [M(CN)(6)](3)(-) anion connects two Ln(3+) using two trans-CN(-) ligands giving rise to a chainlike structure. In the chain, every CuL group tilts toward the CN(-) ligand of adjacent [M(CN)(6)](3)(-) with the Cu-N(cyano) contacts ranging from 2.864(6) to 2.930(6) A. Magnetic studies on the CuGdCo complex (1) indicate the presence of ferromagnetic coupling between Cu(II) and Gd(III). The CuLaCr (5) and CuLaFe (2) complexes exhibit ferromagnetic interaction between paramagnetic Cu(II) and Cr(III)/Fe(III) ions through the weak cyano bridges (Cu-N(cyano) = 2.930(6) A for 2). A global ferromagnetic interaction is operative in the CuGdFe complex (3) with the concurrence of dominant ferromagnetic Cu(II)-Gd(III) and minor antiferromagnetic Gd(III)-Fe(III) as well as the ferromagnetic Cu(II)-Fe(III) interaction. For the CuGdCr complex (4), an overall antiferromagnetic behavior was observed, which is attributed to the presence of dominant antiferromagnetic Cr(III)-Gd(III) coupling and the minor ferromagnetic Cu(II)-Gd(III) and Cu(II)-Cr(III) interaction. Moreover, a spin frustration phenomenon was found in complex 4, which results from the ferro-ferro-antiferromagnetic exchanges in the trigonal Cu-Gd-Cr units. The magnetic susceptibilities of these complexes were simulated using suitable models. The magneto-structural correlation was investigated. These complexes did not show a magnetic phase transition down to 1.8 K.

Pendant macrocyclic metallic building blocks for the design of cyano-bridged heterometallic complexes with 1D chain and 2D layer structures.

A series of cyano-bridged Ni(II)-Cr(I/III) complexes have been synthesized by the reactions of hexaazacyclic Ni(II) complexes with [Cr(CN)(6)](3-) or [Cr(CN)(5)(NO)](3-). Using the tetravalent Ni(II) complex [Ni(H(2)L(2))](4+) (L(2) = 3,10-bis(2-aminoethyl)-1,3,6,8,10,12-hexaazacyclotetradecane), one-dimensional chainlike complexes were produced and subject to magnetic studies, affording the intermetallic magnetic exchange constants of J(1) = +0.23 cm(-1) and J(2) = +8.4 cm(-1) for the complex [Ni(H(2)L(2))][Cr(CN)(5)(NO)]ClO(4).5H(2)O (1) and of J = +5.9 cm(-1) for the complex [Ni(H(2)L(2))](4)[Cr(CN)(6)](5)OH.15H(2)O (2). X-ray diffraction analysis shows that complex 1 has a zigzag chain structure, whereas complex 2 consists of a branched chain structure. Complex 2 exhibits antiferromagnetic ordering at 8.0 K (T(N)). When an octahedral Ni(II) complex cis-[NiL(3)(en)](2+) (en = 1,2-ethylenediamine, L(3) = 3,10-bis(2-hydroxyethyl)-1,3,5,8,10,12-hexaazacyclotetradecane) was used for the synthesis, the common 2D honeycomb-layered complex [NiL(3)](3)[Cr(CN)(5)(NO)](2).8H(2)O (3) was obtained, which has a T(N) value of 3.3 K. Below T(N), a metamagnetic behavior was observed in complexes 2 and 3.

From one-dimensional chain to pentanuclear molecule. Magnetism of cyano-bridged Fe(III)-Ni(II) complexes.

Two cyano-bridged Ni(II)-Fe(III) complexes [(H(3)O)[Ni(H(2)L)](2)[Fe(CN)(6)](2).[Fe(CN)(6)].6H(2)O](n) (1) and [K(18-C-6)(H(2)O)(2)][Ni(H(2)L)](2)[Fe(CN)(6)](3).4(18-C-6).20H(2)O (2) (L = 3,10-bis(2-aminoethyl)-1,3,6,8,10,12-hexaazacyclotetradecane, 18-C-6 = 18-crown-6-ether) have been synthesized and characterized structurally and magnetically. Complex 1 has a zigzag one-dimensional structure, in which two trans-CN(-) ligands of each [Fe(CN)(6)](3)(-) link two trans-[Ni(H(2)L)](4+) groups, and in turn, each trans-[Ni(H(2)L)](4+) links two [Fe(CN)(6)](3)(-) in a trans fashion. Complex 2 is composed of cyano-bridged pentanuclear molecules with moieties connected by the trans-CN(-) ligands of [Fe(CN)(6)](3)(-). Magnetic studies show the existence of ferromagnetic Ni(II)-Fe(III) interactions in both complexes. The intermetallic magnetic coupling constant of both complexes was analyzed by using an approximate model on the basis of the structural features.

Characterization of a soluble molecular magnet: unusual magnetic behavior of cyano-bridged Gd(III)-Cr(III) complexes with one-dimensional and nanoscaled square structures.

Two cyano-bridged Gd(III)-Cr(III) complexes [Gd(urea)(4)(H(2)O)(2)](2)[Cr(CN)(6)](2) (1) and ([Gd(capro)(2)(H(2)O)(4)Cr(CN)(6)].H(2)O)(n)(2) (capro represents caprolactam) have been synthesized and characterized structurally and magnetically. Complex 1 has a tetranuclear Gd(2)Cr(2) square structure, in which two cis-CN(-) ligands of each [Cr(CN)(6)] link two [Gd(urea)(4)(H(2)O)(2)] groups and in turn, two [Gd(urea)(4)(H(2)O)(2)] link two [Cr(CN)(6)] in a cis fashion. Complex 2 is composed of 1D chains with alternating [Gd(capro)(2)(H(2)O)(4)] and [Cr(CN)(6)] moieties connected by the trans-CN(-) ligands of [Cr(CN)(6)]. The dehydration of 2 at 120 degrees C generates a new complex, [Gd(capro)(2)(H(2)O)(2)Cr(CN)(6)] (2'). Magnetic studies show the existence of antiferromagnetic Gd(III)-Cr(III) interaction in these complexes. On the basis of the tetranuclear model, the magnetic susceptibilities of 1 have been analyzed giving the intermetallic magnetic coupling constant of -0.36 cm(-1). Complex 2' exhibits a ferrimagnetic order below 2.1 K. Interestingly, 2' is quite soluble in water, and slow evaporation of the solution gives the hydrated complex 2. Therefore, 2' is a soluble molecular magnet, and this significant behavior implies potential applications. Isothermal magnetization measurements of 2' and other cyano-bridged Gd(III)-Cr(III) molecular magnets show unusual field-induced metamagnetic behavior from the ferrimagnetic ground state to the ferromagnetic state. Field dependence of magnetization of the cyano-bridged Gd(III)-Cr(III) complexes shows unusual field-induced metamagnetic behavior from the ferrimagnetic ground state to the ferromagnetic state.

Tetraaqua-1kappa4O-bis(epsilon -caprolactam-1kappa O)-mu-cyano-1:2kappa 2N:C-pentacyano-2kappa 5C-iron(III)yttrium(III), a novel cyano-bridged dinuclear complex.

Using caprolactam as a ligand, the novel title cyano-bridged yttrium(III)-ferricyanide complex, [Y(caprolactam)(2)(H(2)O)(4)Fe(CN)(6)] or [FeY(CN)(6)(C(6)H(11)NO)(2)(H(2)O)(4)], has been synthesized and structurally characterized. The Y atom is seven-coordinate and has approximately pentagonal-bipyramidal stereochemistry, with water molecules occupying apical positions. Of the five ligands in equatorial positions, one is the N-bound bridging cyano group, and flanking this are two O-bound caprolactam moieties, which are markedly inclined towards the bridged ferricyanide moiety such that they partially envelop it. Water molecules occupy the remaining two equatorial positions. The Y-N-C-Fe-C-N sequence of atoms lies on a crystallographic twofold axis and is therefore perfectly linear, which has not been observed previously in cyano-bridged bimetallic complexes.

Heptairon bis(phosphate) tetrakis(hydrogenphosphate).

A new iron hydrogen phosphate, heptairon bis(phosphate) tetrakis(hydrogenphosphate), Fe(7)(PO(4))(2)(HPO(4))(4), has been prepared hydrothermally and characterized by single-crystal X-ray diffraction. The compound has one Fe atom on an inversion centre and is isostructural with Mn(7)(PO(4))(2)(HPO(4))(4) and Co(7)(PO(4))(2)(HPO(4))(4). The structure is based on a framework of edge- and corner-sharing FeO(6), Fe(5) and PO(4) polyhedra, isotypic with that found in the mixed-valence iron phosphate Fe(7)(PO(4))(6). The Fe atoms in the title compound are purely in the divalent state, just like the Co atoms in Co(7)(PO(4))(2)(HPO(4))(4), the necessary charge balance being maintained by the addition of H atoms in the form of bridging Fe-OH-P groups.