Transition metal complexes of a tridentate ligand bearing two pendant pyridine bases: The X-ray crystal structure of pentacoordinate copper(II) complex

The synthesis of a tridentate ligand, N,N′-bis(2-pyridinyl)-2,6-pyridinedicarboxamide [H₂L] is described together with its manganese(II), cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) complexes which were characterized based on elemental analysis, conductivity measurements, spectral, magnetic and thermal studies. The IR spectral studies of all the complexes exhibit a similar feature about the ligating nature of the ligand to the metal ions and revealed that the ligand has coordinated through the nitrogens of the deprotonated amides and the central pyridine. The two pendant pyridine nitrogens in all the complexes are protonated and involved in hydrogen bonding with the oxygens of amide groups. This observation is confirmed by the single-crystal X-ray crystallographic studies of copper(II) complex. The geometry around the copper atom can be viewed as a distorted trigonal bipyramid with τ = 0.74 [structural parameter, τ = (β − α)/60; where α and β are the two basal angles in a five coordinate complex]. The electrochemical study of the copper(II) complex shows single quasi-reversible redox peak [Cu(II) ↔ Cu(I)]. The EPR spectrum of copper(II) complex exhibits rhombic pattern [g₁ = 2.0276, g₂ = 2.0926 and g₃ = 2.18].     

Comb-shaped graft copolymers with cellulose side-chains prepared via click chemistry

Comb-shaped copolymers with cellobiose acetate or cellulose triacetate (CTA) side-chains, PPMA-g-(CTA2-C15) and PPMA-g-(CTA13-C15), were prepared by grafting N-(15-azidopentadecanoyl)-2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl)-β-d-glucopyranosylamine (CTA2-C15-N₃) and N-(15-azidopentadecanoyl)-tri-O-acetyl-β-cellulosylamine (CTA13-C15-N₃, number average degree of polymerization (DP_n) = 13) onto poly(2-propyn-1-yl methacrylate) (PPMA, weight average degree of polymerization (DP_w, X + Y = 5.59 × 10²)) via “click chemistry”. The copolymers were characterized by ¹H, ¹³C and two-dimensional NMR and size exclusion chromatography-multi-angle laser light scattering (SEC-MALS) measurements. The numbers of CTA side-chains (X) of PPMA-g-(CTA2-C15) and PPMA-g-(CTA13-C15) were calculated as 4.03 × 10² and 2.45 × 10², respectively. Copolymers with cellulosic side-chains, PPMA-g-(CELL2-C15) and PPMA-g-(CELL13-C15), were successfully obtained after deacetylation of PPMA-g-(CTA2-C15) and PPMA-g-(CTA13-C15), respectively. X-ray diffraction measurements revealed that PPMA-g-(CELL13-C15) showed crystalline pattern of cellulose II, which is believed to have anti-parallel orientation.     

Copper(II) complexes as superoxide dismutase mimics: Synthesis, characterization, crystal structure and bioactivity of copper(II) complexes

Two new copper(II) complexes of the type [Cu(L)X₂), where L = (E)-N-phenyl-2-[phenyl (pyridine-2-yl)methylene]hydrazinecarboxamide X = Cl/Br have been synthesized and characterized by elemental analyses, FAB (fast atomic bombardment) magnetic measurements, electronic absorption, conductivity measurements cyclic voltammetry (CV) and Electron paramagnetic resonance (epr) spectroscopy. The structures of these complexes determined by single crystal X-ray crystallography show a distorted square based pyramidal (DSBP) geometry around copper(II) metal center. The distorted CuN₂OX (X = Cl/Br) basal plane in them is comprised of two nitrogen and one oxygen atoms of the meridionally coordinated ligand and a chloride or bromide ion and axial position is occupied by other halide ion. The epr spectra of these complexes in frozen solutions of DMSO showed a signal at g ca. 2. The trend in g-value (g_|| > g_⊥ > 2.00) suggest that the unpaired electron on copper(II) has d_x²-y² character. Biological activities in terms of superoxide dismutase (SOD) and antimicrobial properties of copper(II) complexes have also been measured. The superoxide dismutase activity reveals that these two complexes catalyze the fast disproportionation of superoxide in DMSO solution.     

Synthesis and characterization of a stable paramagnetic hexacoordinated oxochromium(IV) complex with dianionic tetradentate Schiff base ligand salen

A paramagnetic octahedral oxochromium(IV) complex with dianionic tetradentate ligand salen (where H₂salen is N,N′-bis(salicylidene)-1,2-ethylenediamine) has been synthesized. This compound [CrO(OH₂)(salen)] (1) is characterized by elemental analysis, magnetic moment measurement, IR, UV-Vis and EPR spectroscopic studies. Measured room temperature (RT) magnetic moment value is 2.96 BM for 1 indicates a d² system with a triplet ground state. The magnetic moment value rules out a large spin-orbit coupling. The RT and LNT powder EPR spectra of 1 in X-band clearly shows two lines, one around g = 1.965 and the other with larger intensity at g = 4.26 ± 0.10. The first line at g = 1.965 corresponds to the |0> ↔ |±1> transition from the Kramers doublet |±1>, while the broad and intense line at low field with the g-value of 4.26 ± 0.10 is due to the forbidden transition |−1> ↔ |+1>. Compound 1 displays two successive reductions at −0.76 and −1.63 V (versus Ag/AgCl), respectively, while it undergoes only one irreversible oxidation as evident from the well-defined anodic wave at +1.48 V in its cyclic voltammogram.     

A tetracopper(II) complex with N,N′-bis(picolinoyl)hydrazine

Synthesis, physical properties and X-ray structure of a hydrated tetranuclear copper(II) complex [Cu₄(μ-diph)₂(μ-H₂O)₂(O₂CCH₃)₄(H₂O)₂]·4H₂O with N,N′-bis(picolinoyl)hydrazine (H₂diph) are reported. The centrosymmetric complex has two types of copper(II) centres with distorted square-pyramidal N₂O₃ coordination spheres. The dinucleating trans planar diph²⁻ ligands are parallel to each other and act as N₂O-donor to one metal centre and N₂-donor to the other metal centre. The complex has a rectangular {Cu₄(μ-N-N)₂(μ-OH₂)₂} core with Cu···Cu distances as 4.834(1) and 3.762(1) Å. Solid state as well as solution electronic spectra show several transitions in the wavelength range 700-280 nm. The room temperature (298 K) solid state magnetic moment is 3.55 μ_B. The powder EPR spectra at 298 and 130 K are very similar and axial (g_∥ = 2.25 and g_⊥ = 2.08) in character.     

Synthesis of an amphiphilic ruthenium complex with swallow-tail bipyridyl ligand and its application in nc-DSC

An amphiphilic swallow-tail bipyridyl ligand, 4,4′-bis(dihexylmethyl)-2,2′-bipyridine, and its heteroleptic ruthenium (II) complex were synthesized starting from dichloro-(p-cymene)ruthenium (II) dimer. The complex was characterized by UV/Vis and FTIR spectrophotometers, NMR spectroscopy and cyclic voltammetry. The performance of this complex as charge transfer photosensitizer in nc-TiO₂ based dye sensitized solar cells was studied under standard AM 1.5 sunlight and by using an electrolyte consisting of 0.6 M N-methyl-N-butyl imidazolium iodide (BMII), 0.1 M LiI, 0.05 M I₂, 0.5 M 4-tert-butyl pyridine (TBP) in acetonitrile. The complex, CS9 in DMF, gave a photocurrent density of 12.62 mA/cm², 630 mV open circuit potential and 0.62 fill factor yielding 5.68% efficiency.     

A deliberate synthesis of a mononuclear trans-dimethoxide complex of ruthenium(III). X-ray crystal structure, electrochemistry and electron paramagnetic resonance

Using bis(3,5-dimethylpyrazol-1-yl)methane as the bidentate N donor ligand L, the yellow compound trans-[Ru^IIIL₂(OMe)₂]ClO₄ · CH₂Cl₂ is synthesized. It is a rare example of a mononuclear dialkoxo complex of Ru(III). It shows a quasireversible Ru(II/III) couple at −0.65 V versus NHE in acetonitrile at a Pt electrode. Its magnetic moment at room temperature corresponds to one unpaired electron. It displays a rhombic EPR spectrum in acetone at 77 K with g = 2.219, 2.062 and 1.855.     

Synthesis and characterization of platinum(II) complexes of 2N1O-donor ligands with a pendent indole ring

The Pt(II) complexes of 2N1O-donor ligands containing a pendent indole, 3-[N-2-pyridylmethyl-N-2-hydroxy-3,5-di(tert-butyl)benzylamino]ethylindole (Htbu-iepp), and 1-methyl-3-[N-2-pyridylmethyl-N-2-hydroxy-3,5-di(tert-butyl)benzylamino]ethylindole (Htbu-miepp) (H denotes an ionizable hydrogen), were synthesized, and the structure of [Pt(tbu-iepp)Cl] (1) was determined by X-ray analysis. Complex 1 prepared in CH₃CN was revealed to have the C2 atom of the indole ring bound to Pt(II) with the Pt(II)-C2 distance of 1.981(3) Å. On the other hand, [Pt(tbu-miepp)Cl] (2) was concluded to have a phenolate coordination instead of the C2 atom of the indole ring by ¹H NMR spectra. Reaction of 1 with 1 equiv. of Ce(IV) in DMF gave the corresponding one-electron oxidized species, which exhibited an ESR signal at g = 2.004 and an absorption peak at 567 nm, indicating the formation of the Pt(II)-indole-π-cation radical species. The half-life, t_1/2, of the radical species at −60 °C was calculated to be 43 s (k_obs = 1.6 × 10⁻² s⁻¹).     

Trinuclear-based coordination compounds of Mn(II) and Co(II) with 4-amino-3,5-dimethyl-1,2,4-triazole and azide and thiocyanate anions: Synthesis, structure and magnetic properties

A 2D layer complex 1 and a linear trinuclear complex 2 with mixed ligands have been synthesized and characterized by elemental analyses, IR and single-crystal X-ray diffraction. In 1, the Mn(II) ions are six-coordinated and lie in distorted octahedron coordination environments. Complex 1 is connected into a 2D layer structure based on a linear trinuclear Mn₃(admtrz)₄(N₃)₆ (admtrz = 4-amino-3,5-dimethyl-1,2,4-triazole) building unit with either (6,3) topology when Mn1 cations as three-connected nodes or (4,4) network when the coordination trinuclear units being regarded as four connected nodes. In 2, the Co(II) ions are in slightly distorted octahedron coordination geometries. The magnetic behaviors are investigated in the temperature range 1.8-300 K. The magnetic susceptibility measurements show that the Mn(II) ions of complex 1 are weakly antiferromagnetically coupled with g = 1.98(1), J1 = −6.31(5) cm⁻¹ and J2 = −1.88(1) cm⁻¹. There is dominant zero field splitting (ZFS) effects with g values, g_// = 2.38(2) and g_⊥ = 4.96(4), indicated a significant presence of the spin-orbit coupling and magnetization experiment reveals large, uniaxial zero-field splitting parameters of D = −29.55 cm⁻¹ for 2.     

Structure and characterization of a μ-phenoxo-bis μ-acetato dinuclear Mn(II,II) complex [Mn2(LO)(μ-OAc)2](ClO4) (LOH = 2,6-bis{bis(2-(2-pyridyl)ethyl)aminomethyl}-4-methylphenol): Substituent effects

The synthesis, structure and characterization of the dinuclear Mn(II) complex [Mn₂(LO)(μ-OAc)₂](ClO₄) (1) where LOH = 2,6-bis{bis(2-(2-pyridyl)ethyl)aminomethyl)}-4-methylphenol are reported. The reaction of Mn(ClO₄)₂ · 6H₂O with the dinucleating ligand LOH and H₃CCOONa in the presence of NEt₃ in dry, degassed methanol and under an argon atmosphere, yields 1 as a colorless powder. The crystal structure of 1, determined by X-ray diffraction methods, shows a dinuclear Mn(II) complex in which two Mn(II) ions, each in six-coordinate approximate octahedral coordination, are bridged by the phenolate oxygen of LO⁻ and by two acetate ions in a syn,syn-1,3-bridging mode. The Mn-Mn distance is 3.557(1) Å and Mn-O_phenolate-Mn angle is 112.50(9)°. Cyclic voltammetry of 1 in acetonitrile solution shows a quasi-reversible wave at E_1/2 = 0.65 V, for the Mn₂(II,II)/Mn₂(II,III) redox process, and an irreversible oxidation peak at E_p,c = 1.22 V versus Ag/AgCl for the Mn₂(II,III) to Mn₂(III,III) oxidation process. Controlled potential electrolysis of 1 in acetonitrile solution at 0.85 V (versus Ag/AgCl) takes up 1 F of charge per mole of 1 to yield a brown solution of the Mn₂(II,III) state of the complex, which, however, is unstable and reverts back to the Mn₂(II,II) state in solution at room temperature. Least square fitting of the variable temperature magnetic susceptibility measurements on powdered sample of 1 is obtained with g = 1.888, J = −2.75 cm⁻¹, Par = 0.008, TIP = 0. The low −J value and the room temperature calculated magnetic moment of the complex (5.30 BM per Mn(II)), which is less than the spin-only moment of Mn(II), show that the two Mn(II) ions are weakly antiferromagnetically coupled.     

Synthesis, structure, cytotoxic activities and DNA-binding properties of tetracopper(II) complexes with dissymmetrical N,N′-bis(substituted)oxamides as ligands

To compare the cytotoxicities and the DNA-binding properties in tetranuclear complexes with different bridging ligands, two tetracopper(II) complexes with formulae of [Cu₄(oxbe)₂Cl₂(bpy)₂]·4H₂O (1) and [Cu₄(oxbm)₂Cl₂(bpy)₂]·2H₂O (2) were synthesized, where H₃oxbe and H₃oxbm stand for N-benzoato-N′-(2-aminoethyl)oxamide and N-benzoato-N′-(1,2-propanediamine)oxamide, respectively, and bpy is 2,2′-bipyridine. Complex 1 was characterized by elemental analyses, IR and electronic spectra and single-crystal X-ray diffraction. The crystal structure reveals the presence of the circular tetranuclear copper(II) cations which are assembled by a pair of cis-oxamido-bridged dinuclear copper(II) units through carboxyl bridges. The crystal structure of complex 2 has been reported in our previous paper. However, the bioactivities were not studied. Cytotoxicities experiments reveal that both the two complexes exhibit cytotoxic effects against human hepatocellular carcinoma cell SMMC-7721 and human lung adenocarcinoma cell A549, and complex 1 has the better activities than those of complex 2. The results of the interactions between the two complexes and herring sperm DNA (HS-DNA) suggest that the two complexes interact with HS-DNA in the mode of intercalation with the intrinsic binding constants of 3.93 × 10⁴ M⁻¹ (1) and 2.48 × 10⁴ M⁻¹ (2). These results indicated that the bridging ligands may play an important role in the cytotoxicities and the DNA-binding properties of tetranuclear complexes.     

A two-dimensional copper(II) polymer with bridging μ-trans-oxamidate and μ2-picrate ligands: Synthesis, crystal structure and DNA binding studies

A two-dimensional copper(II) polymer with formula of [Cu₂(dmapox)(pic)₂]_n · nCH₃OH, where dmapox is the dianion of N,N′-bis[3-(dimethylamino)propyl]oxamide and pic is picrate, was synthesized and characterized by elemental analysis, conductivity measurement, IR and electronic spectra studies. The crystal structure of the complex has been determined by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P2₁/c with crystallographic data: a = 14.076(7) Å, b = 13.896(7) Å, c = 9.278(5) Å, β = 106.909(6)° and Z = 2. The structure consists of uncoordinated methanol molecules and two-dimensional copper(II) polymeric coordination network constructed by the bis-tridentate trans-dmapox and tridentate picrate ligands. The environment around the copper(II) atom can be described as a distorted octahedron and the Cu?Cu separations through μ-trans-oxamidate and μ₂-picrate bridges are 5.227 Å and 8.359 Å, respectively. The copper(II) complex presents as a polymer in solid state, whereas in solution it presents as discrete neutral binuclear copper(II) species [Cu₂(dmapox)(pic)₂] due to the weak interactions between the copper(II) atoms and the para-nitro oxygens of the adjacent picrate ligands. The fluorescence titration and the ethidium bromide (EB) fluorescence displacement experiments reveal that the binding mode between the binuclear copper(II) complex [Cu₂(dmapox)(pic)₂] and Herring Sperm DNA might be intercalation.     

Coordination modes of N-(2-hydroxyphenyl)methyl-bis-(2-pyridylmethyl)amine with copper (I) and (II) halides

The title ligand, N-(2-hydroxyphenyl)methyl-bis-(2-pyridylmethyl)amine, was prepared via a condensation-reduction synthetic route. The compounds, CuCl(C₁₉H₁₉N₃O) and [CuBr(C₁₉H₁₉N₃O)]⁺Br⁻ · 3H₂O, were readily synthesized from the reaction of CuCl or CuBr₂ and the ligand in acetonitrile. The title copper(I) compound is an O-H ? Cl hydrogen-bonded linear chain of tetrahedrally coordinated copper centers, and the title copper(II) compound exists as two strongly tetragonally distorted dibromide bridged metal cations in a dimer with the phenol hydroxyl groups weakly bound in a trans-fashion to one of the bridging bromides. In the copper(I) complex the phenoxy group acts only as a hydrogen bond donor, whereas in the copper(II) complex it acts both as a ligand and a hydrogen bond donor.     

Copper complexes with new oxaaza-pendant-armed macrocyclic ligands: X-ray crystal structure of a macrocyclic copper(II) complex

The synthesis of new oxaaza macrocyclic ligands (2-4) derived from O¹,O⁷-bis(2-formylphenyl)-1,4,7-trioxaheptane and functionalized tris(2-aminoethyl)amine are described. Mononuclear copper(II) complexes were isolated in the reaction of the corresponding macrocyclic ligand and copper(II) perchlorate. The structure of the [Cu(2)](ClO₄)₂ complex was determined by X-ray diffraction analysis. The copper(II) ion is five-coordinated by all N₅ donor atoms, efficiently encapsulated by the amine terminal pendant-arm, with a trigonal-bipyramidal geometry. The complexes are further characterized by UV-Vis, IR and EPR studies. The electronic reflectance spectra evidence that the coordination geometry for the Cu(II) complexes is trigonal-bipyramidal with the ligands 1 and 2 or distorted square-pyramidal with the ligands 3 and 4. The electronic spectra in MeCN solutions are different from those in the solid state, which suggest that some structural modification may occur in solution. The EPR spectrum of powder samples of the copper complex with 2 presents axial symmetry with hyperfine split at g_// with the copper nuclei (I = 3/2), which is characteristic of weakly exchange coupled extended systems. The EPR parameters (g_// = 2.230, A_// = 156 × 10⁻⁴ cm⁻¹ and g_⊥ = 2.085) indicate a d_x²-y² ground state. The EPR spectra of the complexes with ligands 3 and 4 show EPR spectra with a poorly resolved hyperfine structure at g_//. In contrast, the complex with ligand 2 shows no hyperfine split and a line shape which was simulated assuming rhombic g-tensor (g₁ = 2.030, g₂ = 2.115 and g₃ = 2.190).     

A fluorescent ligand rationally designed to be selective for zinc(II) over larger metal ions. The structures of the zinc(II) and cadmium(II) complexes of N,N-bis(2-methylquinoline)-2-(2-aminoethyl)pyridine

The metal ion coordinating properties of the ligands N,N-bis(2-methylquinoline)-2-(2-aminoethyl)pyridine (DQPEA) and N,N-bis(2-methylquinoline)-2-(2-aminomethyl)pyridine (DQPMA) are presented. DQPEA and DQPMA differ only in that DQPEA forms six-membered chelate rings that involve the pyridyl group, whereas DQPMA forms analogous five-membered chelate rings.These two ligands illustrate the application of a ligand design principle, which states that increase of chelate ring size in a ligand will result in increase in selectivity for smaller relative to larger metal ions. The formation constants (log K₁) of DQPEA and DQPMA with Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II) are reported. As expected from the applied ligand design principle, small metal ions such as Ni(II) and Zn(II) show increases in log K₁ with DQPEA (six-membered chelate ring) relative to DQPMA (five-membered chelate ring), while large metal ions such as Cd(II) and Pb(II) show decreases in log K₁ when the chelate ring increases in size. In order to further understand the steric origin of the destabilization of complexes of metal ions of differing sizes by the six-membered chelate ring of DQPEA, the structures of [Zn(DQPEA)H₂O](ClO₄)₂ (1) [triclinic, , a = 9.2906(10), b = 10.3943(10), c = 17.3880(18) Å, α = 82.748(7)°, β = 88.519(7)°, γ = 66.957(6)°, Z = 4, R = 0.073] and [Cd(DQPEA)(NO₃)₂] (2) [monoclinic, C2/c, a = 22.160(3), b = 15.9444(18), c = 16.6962(18) Å, β = 119.780(3)°, Z = 8, R = 0.0425] are reported. The Zn in (1) is five-coordinate, with a water molecule completing the coordination sphere. The Cd(II) in (2) is six-coordinate, with two unidentate nitrates coordinated to the Cd. It is found that the bonds to the quinaldine nitrogens in the DQPEA complexes are considerably stretched as compared to those of analogous TPyA (tri(pyridylmethyl)amine) complexes, which effect is attributed to the greater steric crowding in the DQPEA complexes. The structures are analyzed for indications of the origins of the destabilization of the complex of the large Cd(II) ion relative to the smaller Zn(II) ion. A possible cause is the greater distortion of the six-membered chelate ring in (2) than in (1), as evidenced by torsion angles that are further away from the ideal values in (2) than in (1). Fluorescence properties of the DQPMA and DQPEA complexes of Zn(II) and Cd(II) are reported. It is found that the DQPEA complex of Zn(II) has increased fluorescence intensity compared to the DQPMA complex, while for the Cd(II) complex the opposite is found. This is related to the greater strain in the six-membered chelate ring of the Cd(II) DQPEA complex as compared to the Zn(II) complex, with resulting poorer overlap in the Cd-N bond, and hence greater ability to quench the fluorescence in the Cd(II) complex.     

Conversion of the g = 4.1 EPR signal to the multiline conformation during the S2 to S3 transition of the oxygen evolving complex of Photosystem II

The oxygen evolving complex of Photosystem II undergoes four light-induced oxidation transitions, S₀-S₁,…,S₃-(S₄)S₀ during its catalytic cycle. The oxidizing equivalents are stored at a (Mn)₄Ca cluster, the site of water oxidation. EPR spectroscopy has yielded valuable information on the S states. S₂ shows a notable heterogeneity with two spectral forms; a g = 2 (S = 1/2) multiline, and a g = 4.1 (S = 5/2) signal. These oscillate in parallel during the period-four cycle. Cyanobacteria show only the multiline signal, but upon advancement to S₃ they exhibit the same characteristic g = 10 (S = 3) absorption with plant preparations, implying that this latter signal results from the multiline configuration. The fate of the g = 4.1 conformation during advancement to S₃ is accordingly unknown. We searched for light-induced transient changes in the EPR spectra at temperatures below and above the half-inhibition temperature for the S₂ to S₃ transition (ca 230 K). We observed that, above about 220 K the g = 4.1 signal converts to a multiline form prior to advancement to S₃. We cannot exclude that the conversion results from visible-light excitation of the Mn cluster itself. The fact however, that the conversion coincides with the onset of the S₂ to S₃ transition, suggests that it is triggered by the charge-separation process, possibly the oxidation of tyr Z and the accompanying proton relocations. It therefore appears that a configuration of (Mn)₄Ca with a low-spin ground state advances to S₃.     

New polymeric thiocyanatoiron(II) complex with N,N′-diethylnicotinamide - Synthesis, structure, magnetic and spectral properties

The iron(II) compound of formula [Fe(NCS)₂(dena)₂]_n (dena = N,N′-diethylnicotinamide) has been prepared by the reaction between iron(III) thiocyanate and dena in ethanol solution. The complex was characterized by elemental analysis, spectral and magnetic measurements. Single-crystal X-ray diffraction methods show that the complex, crystallizing in the triclinic space group, undergoes a phase transition between 220 K and 230 K, connected with the doubling of cell volume. Crystal structures at 230 K (1a; HT phase) and 150 K (1b; LT phase) are described and a transition mechanism is discussed. In both phases the compound has an extended chain structure, in which the neutral molecule of N,N′-diethylnicotinamide acts as a bridging ligand binding through pyridine N atom to one centre and through amide O atom to the neighbouring Fe centre. The Fe²⁺ ion has a slightly distorted trans-octahedral environment with FeO₂N₄ chromophore, and all Fe-O and Fe-N bonds in the typical for high-spin iron(II) compounds range. Variable-temperature magnetic susceptibility data in the temperature range 1.8-300 K show that iron(II) is high-spin S = 2(⁵T_2g) and as a result effects due to zero-field splitting are anticipated at low temperatures. The IR spectrum suggested the coordination of N,N′-diethylnicotinamide to the central atom of iron(II) as a bridging ligand and NCS group as a monodentate ligand.     

Crystal structures and magnetic properties of tetranuclear copper(II) complexes of N-(2-hydroxymethylphenyl)salicylideneimine with a defective double-cubane core

Tetranuclear Cu(II) complexes of N-(2-hydroxymethylphenyl)salicylideneimine (H₂L1-H) and its homologues (5-CH₃: H₂L1-Me, 5-Cl: H₂L1-Cl), [Cu(L1-H)]₄ · 3H₂O (1), [Cu(L1-Me)]₄ · 2CH₂Cl₂ (2), and [Cu(L1-Cl)]₄ · 2CH₂Cl₂ (3), have been characterized by X-ray crystal structure analyses and magnetic measurements. The structure analyses revealed that the complexes 1-3 have a defective double-cubane tetra copper(II) core connected by μ₃-alkoxo bridges. The intramolecular Cu?Cu distances are in the range from 5.251(2)-5.256(3) Å for the longest to 3.0518(9)-3.092(2) Å for the shortest. Each Cu(II) ion has a square-pyramidal geometry and the dihedral angles between adjacent Cu(II) basal planes are almost right angles. Magnetic measurements of the present complexes indicate that weak antiferromagnetic interactions (J=−15 to −19 cm⁻¹) between neighboring copper(II) ions are dominant in these tetracopper cores.     

Electronic spectrum and magnetic properties of a dinuclear nickel(II) complex with two nickel(II) ions of C2-twisted octahedral geometry

A dinickel(II) complex [Ni₂(sym-hmp)₂](BPh₄)₂·3.5DMF·0.5(2-PrOH) (1) was synthesized with a dinucleating ligand, 2,6-bis[(2-hydroxyethyl)methylaminomethyl]-4-methyl-phenol [H(sym-hmp)]. The complex 1 (C₉₀H_118.50B₂N_7.50Ni₂O₁₀) crystallized in the triclinic space group with dimensions a = 14.7446(4) Å, b = 15.4244(4) Å, c = 18.7385(6) Å, α = 86.9495(9)°, β = 76.7263(10)°, γ = 86.5370(8)°, and V = 4136.8(2) Å³ and with Z = 2; this is isomorphous to a previous cobalt(II) complex [Co₂(sym-hmp)₂](BPh₄)₂. Single-crystal X-ray analysis revealed a bis(μ-phenoxo)dinickel(II) core structure containing two distorted octahedral nickel(II) ions of C₂ symmetry. The order of the coordination bond lengths is Ni-O(phenoxo) < Ni-O(hydroxy) < Ni-N. The electronic spectrum of 1 was typical for the octahedral nickel(II) complexes, but the axial elongation and the C₂-twist of the equatorial plane were found after a detailed analysis. The bond angles obtained by the electronic spectrum agreed with the crystallographically obtained bond angles within 2.3°. The order of the AOM parameters was e_{σ,O(phenoxo)} > e_{σ,O(hydroxy)} > e_σ,N, which was consistent with the order of the coordination bond lengths. Magnetic susceptibility data for 1 were fitted well with the parameters 2J = −69.7 cm⁻¹, D = 0.00 cm⁻¹, g = 2.17, and TIP = 265 × 10⁻⁶ cm³ mol⁻¹. The result indicates significant antiferromagnetic exchange interaction and negligible zero-field splitting, while the isostructural cobalt(II) complex showed an anisotropic behavior.     

One-dimensional azido-bridged chiral copper(II) coordination polymers: Syntheses, structures and magnetic studies

Two new one-dimensional azido-bridged chiral copper(II) coordination polymers, [(μ-1,1,3-N₃)₂{Cu₂(R-L)₂(N₃)₂}]_n (1) (R-L = R-2-(N-(2-hydroxybutyl)carbaldimino) pyridine) and [(μ-1,1,3-N₃)₂{Cu₂(S-L)₂(N₃)₂}]_n (2) (S-L = S-2-(N-(2-hydroxybutyl)carbaldimino)pyridine) have been synthesized and structurally characterized. Complexes 1 and 2 crystallize in the monoclinic chiral space group P2₁. For 1, with a = 6.9565(17) Å, b = 20.675(5) Å, c = 9.859(2) Å, β = 105.944(5)° and Z = 2. In the case of compound 2, a = 6.9650(17) Å, b = 20.705(5) Å, c = 9.878(2) Å, β = 105.941(4)° and Z = 2. Both complexes consist of one-dimensional chiral structures in which the copper(II) ions with a distorted octahedral geometry are interlinked by the unusual μ-1,1,3 azido ligands. Circular dichroism spectra demonstrate that 1 and 2 are a pair of enantiomers. Their magnetic properties have been studied. Fitting of the susceptibility data for 1 and 2 using the Bleany-Bowers expression derived from the isotropic spin-exchange Hamiltonian H = −2JS₁S₂ leads to the parameters g = 2.21, J = −2.06 cm⁻¹, zJ′ = −0.0309 cm⁻¹ and R = 4.0 × 10⁻⁴.