New cyanido-bridged iron(II) spin crossover coordination polymers with an unusual ladder-like topology: an alternative to Hofmann clathrates.

Two new cyanido-bridged {FeM} double chains were obtained by reacting cyanido anions [M(CN)] with complex cations [Fe(tptz)] (preformed by mixing a hydrated tetrafluoroborate salt of iron(II) and a tptz ligand, tptz = 2,4,6-tri(2-pyridyl)-1,3,5-triazine) having the general formula [Fe(tptz)M(CN)]·2HO·CHCN, where M = Pd (1) or Pt (2). Additionally, two molecular complexes formulated as [Fe(tptz)][M(CN)]·4.25HO, where M = Pd (3) or Pt (4), were subsequently obtained from the same reaction, as secondary products.

Deciphering the role of water and a zinc-doping process in a polyol-based approach for obtaining Zn/Co/Al-based spinels: toward "green" mesoporous inorganic pigments.

Two new families of zinc/cobalt/aluminum-based pigments, with a unique composition, were obtained through the polyol method. The hydrolysis process of a mixture of Co(CHCOO), Zn(acac) and Al(acac) (acac = acetylacetonate ion) in 1,4-butanediol afforded dark blue gels (wPZnxCo1-xAl), in the presence of a supplementary amount of water, and light green powders (PZnxCo1-xAl), respectively, for the water-free procedure ( = 0, 0.2, 0.

Copper(II) Oxide Nanoparticles Embedded within a PEDOT Matrix for Hydrogen Peroxide Electrochemical Sensing.

The aim of this study is the preparation of nanostructured copper(II) oxide-based materials (CuONPs) through a facile additive-free polyol procedure that consists of the hydrolysis of copper(II) acetate in 1,4-butane diol and its application in hydrogen peroxide sensing. The nonenzymatic electrochemical sensor for hydrogen peroxide determination was constructed by drop casting the CuONP sensing material on top of a glassy carbon electrode (GCE) modified by a layer of poly(3,4-ethylenedioxythiophene) conducting polymer (PEDOT). The PEDOT layer was prepared on GCE using the sinusoidal voltage method.

A rare isostructural series of 3d-4f cyanido-bridged heterometallic squares obtained by assembling [Fe{HB(pz)}(CN)] and Ln ions: synthesis, X-ray structure and cryomagnetic study.

A new series of cyanido-bridged {FeLn} neutral molecular squares of general formula [Fe{HB(pz)}(CN)(μ-CN)Ln(NO)(pyim)(PhPO)]·2CHCN [Ln = Ce (1), Pr (2), Nd (3), Gd (4), Tb (5), Dy (6) and Er (7); {HB(pz)} = hydrotris(pyrazolyl)borate, pyim = 2-(1-imidazol-2-yl)pyridine and PhPO = triphenylphosphine oxide] were obtained by reacting the low-spin [Fe{HB(pz)}(CN)] species with the preformed [Ln(pyim)(NO)(pyim)(PhPO)] complex anions (generated by mixing the nitrate salt of each Ln(III) ion with pyim and PhPO molecules). Single-crystal X-ray diffraction studies show that 1-7 are isostructural compounds that crystallize in the triclinic 1̄ space group. Their crystal structures consist of centrosymmetric cyanido-bridged {FeLn} molecular squares where two [Fe{HB(pz)}(CN)] units adopt bis-monodentate coordination modes towards two [Ln(pyim)(NO)(pyim)(PhPO)] moieties.

In situ generation of PhPO in cyanido-bridged heterometallic {FeLn} molecular squares (Ln = Eu, Sm).

Two new examples of cyanido-bridged {FeLn} molecular squares, with pyim and PPhO as capping ligands at the Ln sites, exhibit weak antiferromagnetic interactions [Ln = Eu (1), Sm (2), pyim = 2-(1H-imidazol-2-yl)pyridine, PPhPO = triphenylphosphine oxide].

Design of 3d-4f molecular squares through the [Fe{(HB(pz))}(CN)] metalloligand.

A new series of {FeIII2LnIII2} heterobimetallic squares of general formula [FeIII{HB(pz)3}(CN)(μ-CN)2Ln(pyim)x(NO3)2(H2O)y]2·zH2O [Ln = La (1), Gd (2), Tb (3) and Dy (4); {HB(pz)3}- = hydrotris(pyrazolyl)borate and pyim = 2-(1H-imidazol-2-yl)pyridine; x = 2, y = 0 (1), x = y = 1 (2-4) and z = 10 (1), 6 (2), 2.76 (3), 4 (4)] were synthesized by reacting the low-spin [FeIII{HB(pz)3}(CN)3]- complex anion with the preformed [LnIII(pyim)x(NO3)2(H2O)y]+ complex cation [formed in situ by mixing the lanthanide(iii) salt and the pyim ligand]. Single-crystal X-ray diffraction shows that 1-4 crystallize in the P1[combining macron] triclinic space group, 2-4 being isomorphous.

Three different types of bridging ligands in a 3d-3d'-3d'' heterotrimetallic chain.

A one-pot synthesis of a 3d-3d'-3d'' heterotrimetallic coordination polymer with double diphenoxido, single cyanido and bis-bidentate oxalate as alternating bridges which exhibits an overall antiferromagnetic behaviour has been developed.

Cyanido-Bridged {LnW} Heterobinuclear Complexes: Synthesis and Magneto-Structural Study.

A new series of cyanido-bridged {LnW} heterobinuclear complexes of formula [Ln(pyim)(i-PrOH)(HO)(μ-CN)W(CN)]·2HO [Ln = Gd (1), Tb (2), Dy (3), Ho (4), and Er (5); pyim = 2-(1H-imidazol-2-yl)-pyridine) and i-PrOH = isopropyl alcohol] were synthesized by one-pot reaction between (NHBu)[W(CN)] and [Ln(pyim)] complexes (generated in situ by mixing the corresponding Ln ions and the pyim ligand). Compounds 1-5 are isomorphous and crystallize in the monoclinic system P2/n space group. Their crystal structure consists of binuclear units in which the octacyanotungstate(V) anion coordinates to the corresponding Ln ion through a single cyanide ligand.

Synthesis, Crystal Structures, and Magnetic Properties of Two Novel Cyanido-Bridged Heterotrimetallic {CuMnCr} Complexes.

The self-assembly process between the heteroleptic [Cr(phen)(CN)] and [Cr(ampy)(CN)] metalloligands and the heterobimetallic {Cu(valpn)Mn} tecton afforded two heterotrimetallic complexes of formula [{Cu(valpn)Mn(μ-NC)Cr(phen)(CN)}{(μ-NC)Cr(phen)(CN)}]·2CHCN (1) and {[Cu(valpn)Mn(μ-NC)Cr(ampy)(CN)]·2CHCN} (2) [phen = 1,10-phenanthroline, ampy = 2-aminomethylpyridine, and Hvalpn = 1,3-propanedyilbis(2-iminomethylene-6-methoxyphenol)]. The crystal structure of 1 consists of neutral CuMnCr octanuclear units, where two [Cr(phen)(CN)] anions act as bis-monodentate ligands through cyanide groups toward two manganese(II) ions from two [Cu(valpn)Mn] units to form a [{Cu(valpn)Mn}Cr(CN)] square motif. Two [Cr(phen)(CN)] pendant anions in 1 are bound to the copper(II) ions with cis-trans geometry with respect to the bridging [Cr(phen)(CN)] anion.

Synthesis, crystal structure and magnetic properties of a cyanide-bridged heterometallic {CoMn} chain.

The assembly reaction between the low-spin [Co(dmphen)(CN)] metalloligand and the [Mn(salen)(HO)] complex cation yielded the one-dimensional compound {[Mn(salen)(μ-NC)Co(dmphen)(CN)]·2HO} (1), which behaves as a ferrimagnetic chain, the intrachain magnetic coupling being J = -1.71(1) cm.

A new family of [Cu(II)Ln(III)M(V)] heterotrimetallic complexes (Ln = La, Gd, Tb; M = Mo, W): model systems to probe exchange interactions and single-molecule magnet properties.

Four isostructural trinuclear 3d-4f-4(5)d heterotrimetallic complexes, with the general formula [L(2)CuLn(H2O)5(μ-NC)M(CN)7], were obtained from the association of binuclear 3d-4f complexes and {M(V)(CN)8}(3-) metalloligands (M = Mo, Ln = La ; M = W, Ln = La ; M = Mo, Ln = Gd ; M = Mo; Ln = Tb , where H2L(2) = 1,2-ethanediylbis(2-iminomethylene-6-methoxy-phenol)). The metalloligand coordinates through a single-cyanido group at the apical position of the copper(ii) ion belonging to the {Cu(II)Ln(III)} binuclear complex. The analysis of the magnetic data for the La(iii) derivatives (compounds and ), in the 1.

Crystal structure of tris-(μ-bis-{4-[(pyridin-2-yl-methyl-idene)amino]-phen-yl}methane-κ(4) N,N':N'',N''')dizinc tetra-kis-(tetra-fluorido-borate) aceto-nitrile tris-olvate.

The asymmetric unit of the title compound, [Zn2(C25H20N4)3](BF4)4·3CH3CN, consists of one dinuclear Zn(II) complex cation with a triple-helical [Zn2 L 3](4+) motif (L is bis-{4-[(pyridin-2-yl-methyl-idene)amino]-phen-yl}methane), four BF4 (-) anions and three CH3CN solvent mol-ecules. The Zn⋯Zn separation is 11.3893 (14) Å and the ligands wrap around the two Zn(II) atoms, forming a triple helix as defined by the Zn-N-N-Zn torsion angles of 104.

Magneto-structural variety of new 3d-4f-4(5)d heterotrimetallic complexes.

Three families of heterotrimetallic chains (type 1-type 3), with different topologies, have been obtained by reacting the 3d-4f complexes, [{Cu(L(1))}xLn(NO3)3] with x = 1 or 2, formed in situ by the reaction of Schiff-base bi-compartmental [Cu(II)(L(1))] complexes and lanthanide(iii) salts, with (NHBu3)3[M(CN)8] (M = Mo(V), W(V)). For type 1 series of compounds, 1-D coordination polymers, with the general formula [{Cu2(valpn)2Ln}{M(CN)8}]·nH2O·mCH3CN (where H2valpn = 1,3-propanediylbis(2-iminomethylene-6-methoxy-phenol), result from the association of trinuclear {CuLn(III)} moieties and [M(V)(CN)8](3-) anions acting as tri-connecting spacers [Ln = La (1), Ce (2), Eu (3), Tb (4), Ho (5), M = Mo; Ln = Tb (6), Ho (7), M = W; m = 0, n = 1.5 (7) and 2 (1-4, 6); n = 1, m = 1 (5)].

Two-dimensional coordination polymers constructed by [Ni(II)Ln(III)] nodes and [W(IV)(bpy)(CN)6]2- spacers: a network of [Ni(II)Dy(III)] single molecule magnets.

Three isomorphous two-dimensional (2D) coordination polymers of general formula {[Ni(II)(valpn)Ln(III)(NO3)(H2O)(μ-NC)4W(IV)(bipy)(CN)2]·xH2O·yCH3CN}n have been synthesized by reacting Ph4P[W(V)(CN)6(bipy)] with the heterodinuclear [Ni(II)Ln(III)(valpn)(O2NO)3] complexes [H2valpn = 1,3-propanediyl-bis(2-iminomethylene-6-methoxyphenol), bipy = 2,2'-bipyridine, and Ln = Gd (1), Dy (2), and Tb (3) with x = 2 (1), 3.9 (2), and 3.35 (3) and y = 2.

Self-assembly of [Cu(II)Tb(III)]3+ and [W(CN)8]3- tectons: a case study of a mixture containing two complexes showing slow-relaxation of the magnetization.

The reaction of [Cu(valen)] with Tb(NO(3))(3) and (Bu(3)NH)(3)[W(CN)(8)] affords two types of crystals: [{W(CN)(8)}Cu(valen)Tb(OH(2))(5)]·2H(2)O (1, a discrete trinuclear complex) and [{W(CN)(8)}Cu(valen)Tb(OH(2))(4)]·CH(3)CN·H(2)O (2, an infinite zig-zag chain), both compounds showing slow relaxation of the magnetization (H(2)valen is the Schiff base resulting from the reaction of o-vanillin with 1,2-ethanediamine).

[W(bipy)(CN)6]-: a suitable metalloligand in the design of heterotrimetallic complexes. The first Cu(II)Ln(III)W(V) trinuclear complexes.

The first 3d-4f-5d heterotrimetallic complexes using [W(V)(bipy)(CN)(6)](-) as a metalloligand were synthesized (bipy = 2,2'-bipyridine). The structural and magnetic properties of three [Cu(II)Ln(III)W(V)] complexes (Ln = Gd, Ho, Tb) are discussed.