Dinuclear complexes of M-II thiocyanate (M = Ni and Cu) containing a tridentate Schiff-base ligand: synthesis, structural diversity and magnetic properties

A dinuclear Ni-II complex, [Ni-2(L)(2)(H2O)(NCS)(2)]center dot 3H(2)O (1) in which the metal atoms are bridged by one water molecule and two mu(2)-phenolate ions, and a thiocyanato-bridged dimeric Cull complex, [Cu(L)NCS](2) (2) [L = tridentate Schiff-base ligand, N-(3-aminopropyl)salicylaldimine, derived from 1:1 condensation of salicylaldehyde and 1,3-diaminopropane], have been synthesized and characterized by IR and UV/Vis spectroscopy, cyclic voltammetry and single-crystal X-ray diffraction studies. The structure of 1 consists of dinuclear units with crystallographic C-2 symmetry in which each Ni-II atom is in a distorted octahedral environment. The Ni-O distance and the Ni-O-Ni angle, through the bridged water molecule, are 2.240(11) angstrom and 82.5(5)degrees, respectively. The structure of 2 consists of dinuclear units bridged asymmetrically by di-mu(1,3)-NCS ions; each Cull ion is in a square-pyramidal environment with tau = 0.25. Variable-temperature magnetic susceptibility studies indicate the presence of dominant ferromagnetic exchange coupling in complex 1 with J = 3.1 cm(-1), whereas complex 2 exhibits weak antiferromagnetic coupling between the Cu-II centers with J = -1.7 cm(-1). ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

Ternary erbium chromium sulfides : structural relationships and magnetic properties

Single crystals of four erbium-chromium sulfides have been grown by chemical vapor transport using iodine as the transporting agent. Single-crystal X-ray diffraction reveals that in Er(3)CrS(6) octahedral sites are occupied exclusively by Cr(3+) cations, leading to one-dimensional CrS(4)(5-) chains of edge-sharing octahedra, while in Er(2)CrS(4), Er(3+), and Cr(2+) cations occupy the available octahedral sites in an ordered manner. By contrast, in Er(6)Cr(2)S(11) and Er(4)CrS(7), Er(3+) and Cr(2+) ions are disordered over the octahedral sites. In Er(2)CrS(4), Er(6)Cr(2)S(11), and Er(4)CrS(7), the network of octahedra generates an anionic framework constructed from M(2)S(5) slabs of varying thickness, linked by one-dimensional octahedral chains. This suggests that these three phases belong to a series in which the anionic framework may be described by the general formula [M(2n+1)S(4n+3)](x-), with charge balancing provided by Er(3+) cations located in sites of high-coordination number within one-dimensional channels defined by the framework. Er(4)CrS(7), Er(6)Cr(2)S(11), and Er(2)CrS(4) may thus be considered as the n = 1, 2, and infinity members of this series. While Er(4)CrS(7) is paramagnetic, successive magnetic transitions associated with ordering of the chromium and erbium sub-lattices are observed on cooling Er(3)CrS(6) (T(C)(Cr) = 30 K; T(C)(Er) = 11 K) and Er(2)CrS(4) (T(N)(Cr) = 42 K, T(N)(Er) = 10 K) whereas Er(6)Cr(2)S(11) exhibits ordering of the chromium sub-lattice only (T(N) = 11.4 K).

A new cyano-bridged one-dimensional (GdFeIII)-Fe-III coordination polymer with o-phenanthroline as the blocking ligand: synthesis, structure, and magnetic properties

Synthesis, structural characterization, and magnetic properties of a new cyano-bridged one-dimensional iron (III)-gadolinium (III) compound, trans-[Gd(o-phen)(2)(H2O)(2)(mu-CN)(2)Fe(CN)(4)], - 2no-phen (o-phen = 1,10-phenanthroline), have been described. The compound crystallizes in the triclinic P (1) over bar space group with the following unit cell parameters: a = 10.538(14) angstrom, b = 12.004(14) angstrom, c = 20.61(2) angstrom, alpha = 92.41(1)degrees, beta = 92.76(1)degrees, gamma = 11 2.72(1)degrees, and Z = 2. In this complex, each gadolinium (III) is coordinated to two nitrile nitrogens of the CN groups coming from two different ferricyanides, the mutually trans cyanides of each of which links another different Gd-III to create -NC-Fe(CN)(4)-CN-Gd-NC- type 1-D chain structure. The one-dimensional chains are self-assembled in two-dimensions via weak C-H center dot center dot center dot N hydrogen bonds. Both the variable-temperature (2-300 K, 0.01 T and 0.8 T) and variable-field (0-50 000 Gauss, 2 K) magnetic measurements reveal the existence of very weak interaction in this molecule. The temperature dependence of the susceptibilities has been analyzed using a model for a chain of alternating classic (7/2) and quantum (1/2) spins. (c) 2005 Elsevier B.V. All rights reserved.

Facile strategies for the synthesis and crystallization of linear trinuclear nickel(II)-Schiff base, complexes with carboxylate bridges: Tuning of coordination geometry and magnetic properties

Three new linear trinuclear nickel(II) complexes, [Ni-3(salpen)(2)(OAc)(2)(H2O)(2)]center dot 4H(2)O (1) (OAc = acetate, CH3COO-), [Ni-3(salpen)(2)(OBz)(2)] (2) (OBz=benzoate, PhCOO-) and [Ni-3(salpen)(2)(OCn)(2)(CH3CN)(2)] (4) (OCn = cinnamate, PhCH=CHCOO-), H(2)salpen = tetradentate ligand, N,N'-bis(salicylidene)-1,3-pentanediamine have been synthesized and characterized structurally and magnetically. The choice of solvent for growing single crystal was made by inspecting the morphology of the initially obtained solids with the help of SEM study. The magnetic properties of a closely related complex, [Ni-3(salpen)(2)(OPh)(2)(EtOH)] (3) (OPh = phenyl acetate, PhCH2COO-) whose structure and solution properties have been reported recently, has also been studied here. The structural analyses reveal that both phenoxo and carboxylate bridging are present in all the complexes and the three Ni(II) atoms remain in linear disposition. Although the Schiff base ligand and the syn-syn bridging bidentate mode of the carboxylate group remain the same in complexes 1-4, the change of alkyl/aryl group of the carboxylates brings about systematic variations between six- and five-coordination in the geometry of the terminal Ni(II) centres of the trinuclear units. The steric demand as well as hydrophobic nature of the alkyl/aryl group of the carboxylate is found to play a crucial role in the tuning of the geometry. Variable-temperature (2-300 K) magnetic susceptibility measurements show that complexes 1-4 are antiferromagnetically coupled (J = -3.2(1), -4.6(1). -3.2(1) and -2.8(1) cm(-1) in 1-4, respectively). Calculations of the zero-field splitting parameter indicate that the values of D for complexes 1-4 are in the high range (D = +9.1(2), +14.2(2), +9.8(2) and +8.6(1) cm(-1) for 1-4, respectively). The highest D value of +14.2(2) and +9.8(2) cm(-1) for complexes 2 and 3, respectively, are consistent with the pentacoordinated geometry of the two terminal nickel(II) ions in 2 and one terminal nickel(II) ion in 3. (C) 2009 Elsevier Ltd. All rights reserved.

A unique example of structural and magnetic diversity in four interconvertible copper(II)−azide complexes with the same Schiff base ligand: a monomer, a dimer, a chain, and a layer

Four new Cu(II)-azido complexes of formula [CuL(N-3)] (1), [CuL(N-3)](2) (2), [Cu7L2(N-3)(12)](n) (3), and [Cu2L(dmen)-(N-3)(3)](n) (4) (dmen = N,N-dimethylethylenediamine) have been synthesized using the same tridentate Schiff base ligand HL (2-[1-(2-dimethylaminoethylimino)ethyl]phenol, the condensation product of dmen and 2-hydroxyacetophenone). The four compounds have been characterized by X-ray structural analyses and variable-temperature magnetic susceptibility measurements. Complex 1 is mononuclear, whereas 2 is a single mu-1,1 azido-bridged dinuclear compound. The polymeric compound 3 possesses a 2D structure in which the Cu(II) ions are linked by phenoxo oxygen atoms and two different azide bridges (mu-1,1 and mu-1,1,3). The structure of complex 4 is a double helix in which two mu-1,3-azido-bridged alternating one-dimensional helical chains of CuL(N-3) and Cu(dmen)(N-3)(2) are joined together by weak mu-1,1 azido bridges and H-bonds. The complexes interconvert in solution and can be obtained in pure form by carefully controlling the conditions. The magnetic properties of compounds 1 and 2 show the presence of very weak antiferromagnetic exchange interactions mediated by a ligand pi overlap (J = -1.77) and by an asymmetric 1,1-N-3 bridge (J = -1.97 cm(-1)), respectively. Compound 3 presents, from the magnetic point of view, a decorated chain structure with both ferro- and antiferromagnetic interactions. Compound 4 is an alternating helicoidal chain with two weak antiferromagnetic exchange interactions (J -1.35 and -2.64 cm(-1)).

Synthesis, crystal structures and magnetic properties of two bis(μ-phenoxido)dicopper(II) complexes derived from reduced Schiff base ligands

Two phenoxido bridged dinuclear Cu(II) complexes, [Cu-2(L-1)(2)(NCNCN)(2)] (1) and [Cu-2(L-2)(2)(NCNCN)(2)]center dot 2H(2)O (2) have been synthesized using the tridentate reduced Schiff-base ligands 2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol (HL1) and 2-[1-(3-methylamino-propylamino)-ethyl]-phenol (HL2), respectively. The complexes have been characterized by X-ray structural analyses and variable-temperature magnetic susceptibility measurements. Both the complexes present a diphenoxido bridging Cu2O2 core. The geometries around metal atoms are intermediate between trigonal bipyramid and square pyramid with the Addison parameters (tau) = 0.57 and 0.49 for 1 and 2, respectively. Within the core the Cu-O-Cu angles are 99.15 degrees and 103.51 degrees and average Cu-O bond distances are 2.036 and 1.978 angstrom for compounds 1 and 2, respectively. These differences have marked effect on the magnetic properties of two compounds. Although both are antiferromagnetically coupled, the coupling constants (J = -184.3 and -478.4 cm (1) for 1 and 2, respectively) differ appreciably.

Synthesis, crystal structure, and magnetic properties of a very rare double μ-1,1-azido- and a μ-1,1-(OMe)-bridged FeIII dimer containing a N,N,O-donor tridentate Schiff base ligand

Two new Fe-III complexes, [Fe2L2(mu-OMe)(2)(NCS)(2)] (1) and [Fe2L2(mu-N-3)(2)(N-3)(2)] (2), have been synthesized using a N,N,O-donor tridentate Schiff base ligand HL {2-[(2-dimethylaminoethylimino)methyl]phenol}, the condensation product of salicylaldehyde and N,N-dimethyl-1,2-diaminoethane. The complexes were characterized by X-ray structural analyses and variable-temperature magnetic susceptibility measurements. Both crystal structures are centrosymmetric dimers containing two Fe-III atoms, which are bridged in compound 1 by two methoxy anions and in compound 2 by two mu-1,1-azides. The chelating tridentate Schiff base and a terminal thiocyanato (for 1) or azido (for 2) group complete the hexacoordination of the distorted octahedral environment of each iron center. The magnetic properties of compound 1 show the presence of antiferromagnetic exchange interactions mediated by double methoxy bridges (J = -29.45 cm(-1)). Compound 2 shows the presence of very weak ferromagnetic exchange interactions mediated by double mu-1,1-N-3 bridges (J = 1.08 cm(-1)).

Synthesis, crystal structures and magnetic properties of a phenoxo-bridged dinuclear Cu(II) complex and a dicyanamide bridged novel molecular rectangle based on it

The phenoxo-bridged dinuclear Cu-II complex [Cu2L2-(NCNCN)(2)] (1) and the dicyanamide-bridged molecular rectangle [Cu4L4{mu(1,5)-(NCNCN)(2)}]center dot(ClO4)(2)(H2O)(2) (2) were synthesized using the tridentate reduced Schiff-base ligand HL {2-[(2-dimethylamino-ethylamino) methyl] phenol}. The complexes were characterized by X-ray structural analyses and variable-temperature magnetic susceptibility measurements. Complex 2 was formed through the joining of the phenoxo-bridged dinuclear Cu2O2 cores of 1 via the mu(1,5)-bridging mode of dicyanamide. The structural properties of the Cu2O2 cores in two complexes are significantly different. The geometry of the copper ions is distorted trigonal bipyramid in 1 but is nearly square-pyramidal in 2. These differences have a marked effect on the magnetic properties of two compounds. Although both are antiferromagnetically coupled, the coupling constants (J = -185.2 and -500.9 cm(-1) for 1 and 2, respectively) differ considerably.

Structure and magnetic properties of polydisperse ferrofluids: a molecular dynamics study

We study by Langevin molecular dynamics simulations systematically the influence of polydispersity in the particle size, and subsequently in the dipole moment, on the physical properties of ferrofluids. The polydispersity is in a first approximation modeled by a bidisperse system that consists of small and large particles at different ratios of their volume fractions. In the first part of our investigations the total volume fraction of the system is fixed, and the volume fraction phi(L) of the large particles is varied. The initial susceptibility chi and magnetization curve of the systems show a strong dependence on the value of phi(L). With the increase of phi(L), the magnetization M of the system has a much faster increment at weak fields, and thus leads to a larger chi. We performed a cluster analysis that indicates that this is due to the aggregation of the large particles in the systems. The average size of these clusters increases with increasing phi(L). In the second part of our investigations, we fixed the volume fraction of the large particles, and increased the volume fraction phi(S) of the small particles in order to study their influence on the chain formation of the large ones. We found that the average aggregate size formed by large particles decreases when phi(S) is increased, demonstrating a significant effect of the small particles on the structural properties of the system. A topological analysis of the structure reveals that the majority of the small particles remain nonaggregated. Only a small number of them are attracted to the ends of the chains formed by large particles.

Facile synthesis of Cu(II) complexes of monocondensed N,N,N donor Schiff base ligands: crystal structure, spectroscopic and magnetic properties

Four new copper(II) complexes, [((CuLN3)-N-1)(2)](ClO4)(2) (1), [(CuL2 N-3)(2)](ClO4)(2) (2), [CuL3(N-3)ClO4)](n) (3) and [CuL4(mu-1,1-N-3)(mu-1,3-N-3)(ClO4)](n) (4) where L-1 = N-1-pyridin-2-yl-methylene-propane-1,3-diamine, L-2 = N-1-(1-pyridin-2-yl-ethylidene)propane-1,3-diamine, L-3 =N-1-(1-pyridin-2-yl-ethylidene)ethane-1,2-diamine and L-4=N-1-(1-pyridin-2-yl-ethylidene)propane-1,2-diamine are four tridentate N,N,N donor Schiff base ligands, have been derived and structurally characterized by X-ray crystallography. Compounds 1 and 2 consist of double basal-apical end-on (EO) azide bridged dinuclear Cu-II complexes with square-pyramidal geometry. In complex 3 the square planar mononuclear [CuL3 (N-3)] units are linked by weakly coordinated perchlorate ions in the axial positions of Cu-II to form a one-dimensional chain. Two such chains are connected by hydrogen bonds involving perchlorate ions and azide groups. Compound 4 consists of 1-D chains in which the Cu-II ions with a square-pyramidal geometry are alternately bridged by single EO and end-to-end (EE) azido ligands, both adopting a basal-apical disposition. Variable temperature (300-2 K) magnetic susceptibility measurements and magnetization measurements at 2 K have been performed. The results reveal that complexes 1 and 2 are antiferromagnetically coupled through azido bridges (J= -12.18 +/- 0.09 and -4.43 +/- 0.1 cm(-1) for 1 and 2, respectively). Complex 3 shows two different magnetic interactions through the two kinds of hydrogen bonds; one is antiferromagnetic (J(1) = - 9.69 +/- 0.03 cm(-1)) and the other is ferromagnetic (J(2) = 1.00 +/- 0.01 cm(-1)). From a magnetic point of view complex 4 is a ferromagnetic dinuclear complex (J= 1.91 +/- 0.01 cm(-1)) coupled through the EO bridge only. The coupling through the EE bridge is practically nil as the N(azido)-Cu-II (axial) distance (2.643 angstrom) is too long. (C) 2006 Elsevier Ltd. All rights reserved.

Syntheses, crystal structures and magnetic properties of carboxylato-bridged polymeric networks of Mn-II

Three new carboxylato-bridged polymeric networks of Mn-II having molecular formula [Mn(ox)(dpyo)](n) (1), {[Mn-2(mal)(2)(bpee)(H2O)(2)]center dot 0.5(bpee)center dot 0.5(CH3OH)}n, (2) and {[Mn-3(btc)(2)(2,2'-bipy)(2)(H2O)(6)]center dot 4H(2)O}(n) (3) [dpyo, 4,4'-bipyridine N,N'dioxide; bpee, trans-1,2 bis(4-pyridyl) ethylene; 2,2'-bipy, 2,2'-bipyridine; ox = oxalate dianion; mal = malonate dianion; btc = 1,3,5-benzenetricarboxylate trianion] have been synthesized and characterized by single-crystal X-ray diffraction studies and low temperature magnetic measurements. Structure determination of complex I reveals a covalent bonded 2D network containing bischelating oxalate and bridging dpyo; complex 2 is a covalent,bonded 3D polymeric architecture, formed by bridging malonate and bpee ligands, resulting in an open framework with channels filled by uncoordinated disordered bpee and methanol molecules. Whereas complex 3, comprising btc anions bound to three metal centers, is a 1D chain which further extends its dimensionality to 3D via pi-pi and H-bonding interactions. Low temperature magnetic measurements reveal the existence of weak antiferromagnetic interaction in all these complexes. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006).

Influence of counter anions on the structures and magnetic properties of trinuclear Cu(II) complexes containing a mu(3)-OH core and Schiff base ligands

Four trinuclear Cu(II) complexes, [(CuL1)(3)(mu(3)-OH)](NO3)(2) (1), [(CuL2)(3)(mu(3)-OH)](I)(2)center dot H2O (2), [(CuL3)(3)(mu(3)-OH)](I)(2) (3) and [(CuL1)(3)(mu(3)-OH)][(CuI3)-I-1] (4), where HL1 (8-amino-4-methyl-5-azaoct-3-en-2-one), HL2 [7-amino-4-methyl-5-azaoct-3-en-2-one] and HL3 [7-amino-4-methyl-5-azahept-3-en-2- one] are the three tridentate Schiff bases, have been synthesized and structurally characterized by X-ray crystallography. All four complexes contain a partial cubane core, [(CuL)(3)(mu(3)-OH)](2+) in which the three [CuL] subunits are interconnected through two types of oxygen bridges afforded by the oxygen atoms of the ligands and the central OH- group. The copper(II) ions are in a distorted square-pyramidal environment. The equatorial plane consists of the bridging oxygen of the central OH- group together with three atoms (N, N, O) from the Schiff base. The oxygen atom of the Schiff base also coordinates to the axial position of Cu(II) of another subunit to form the cyclic trimer. Magnetic susceptibilities have been determined for these complexes over the temperature range of 2-300 K. The isotropic Hamiltonian, H = -J(12)S(1)S(2) - J(13)S(1)S(3) - J(23)S(2)S(3) has been used to interpret the magnetic data. The best fit parameters obtained are: J = - 54.98 cm(-1) g = 2.24 for 1; J = - 56.66 cm(-1), g = 2.19 for 2; J = -44.39 cm(-1), g = 2.16 for 3; J = - 89.92 cm(-1), g = 2.25 for 4. The EPR data at low temperature indicate that the phenomenon of spin frustration occurs for complexes 1-3. (c) 2007 Elsevier B.V. All rights reserved.

The Crucial Role of Polyatomic Anions in Molecular Architecture: Structural And Magnetic Versatility of Five Nickel(II) Complexes Derived from A N,N,O-Donor Schiff Base Ligand

A series of five Ni(II)-complexes containing the same tridentate Schiff base but different monoanionic ligands (N-3(-), NO3-, PhCOO- and NO2-)reveals that the competitive as well as the cooperative role of the monoanions and phenoxo group in bridging the metal ions play the key role in the variation of molecular architecture.

Structural and spectroscopic properties of Ru(II) complexes of 4-(aryl)thiosemicarbazones of thiophen-2-carbaldehyde

Six Ru(II) complexes of formula [Ru(L)(2)(PPh3)(2)] have been prepared where LH = 4-(aryl)thiosemicarbazones of thiophen-2-carbaldehyde. X-ray crystal structures of five of the complexes are reported. In all the complexes ruthenium is six coordinate with a distorted octahedral cis-P-2, cis-N-2, trans-S-2 donor environment, and each of the two thiosemicarbazone ligands are coordinated in a bidentate fashion forming a four membered chelate ring. The complexes undergo a one-electron oxidation at similar to 0.5 V vs. Ag/AgCl. The EPR spectrum of the electrochemically oxidized solution at 100 K shows a rhombic signal, with transitions at g(1) = 2.27, g(2) = 2.00 and g(3) = 1.80. DFT calculations on one of the complexes suggest that there is 35% ruthenium and 17% sulfur orbital contribution to the HOMO. These results suggest that the assignment of metal atom oxidation states in these compounds is not unambiguous. (C) 2009 Elsevier Ltd. All rights reserved.

Trinuclear cu(ll) complexes containing peripheral ketonic oxygen bridges and a mu(3)-OH core: Syntheses, crystal structures, spectroscopic and magnetic properties

Four new trinuclear copper(II) complexes, [(CuL1)(3)(mu(3)-OH)](ClO4)(2)center dot H2O (1), [(CuL2)(3)(mu(3)-OH)](CIO4)(2) (2), [(CuL3)(3)-(mu(3)-OH)](ClO4)(4)center dot H2O (3), and [(CuL4)(3)(mu(3)-OH)](ClO4)(2)center dot H2O (4), where HL1 = 8-amino-4,7,7-trimethyl-5-azaoct-3-en-2-one, HL2 = 7-amino-4-methyl-5-azaoct-3-en-2-one, HL3 = 7(ethylamino)-4-methyl-5-azahept-3-en-2-one, and HL4 = 4-methyl-7-(methylamino)-5-azahept-3-en-2-one, have been derived from the four tridentate Schiff bases (HL1, HL2, HL3, and HL4) and structurally characterized by X-ray crystallography. For all compounds, the cationic part is trinuclear with a CU3OH core held by three carbonyl oxygen bridges between each pair of copper(II) atoms. The copper atoms are five-coordinate with a distorted square-pyramidal geometry; the equatorial plane consists of the bridging oxygen atom of the central OH group together with three atoms (N, N, O) from one ligand whereas an oxygen atom of a second ligand occupies the axial position. Magnetic measurements have been performed in the 2-300 K temperature range. The experimental data could be satisfactorily reproduced by using an isotropic exchange model, H = -J(S1S2+S2S3+S1S3) yielding as best-fit parameters: J = -66.7 and g = 2.19 for 1, J = -36.6 and g = 2.20 for 2, J = -24.5 and g = 2.20 for 3, and J = -14.9 and g = 2.05 for 4. EPR spectra at low temperature show the existence of spin frustration in complexes 3 and 4, but it has not been possible to carry out calculations of the antisymmetric exchange parameter, G, from magnetic data. In frozen methanolic solution, at 4 K, hyperfine splitting in all complexes and spin frustration in complex 4 seem to be confirmed. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)