Synthesis of unsymmetrical compartmental oxime nickel(II) and copper(II) complexes: spectral, electrochemical and magnetic studies

A new series of binuclear unsymmetrical compartmental oxime complexes (1–5) [M₂L] [M=Cu(II), Ni(II)] have been synthesized using mononuclear complex [ML] (L=1,4-bis[2-hydroxy-3-(formyl)-5-methylbenzyl]piperazine), hydroxylamine hydrochloride and triethylamine. In this system there are two different compartments, one has piperazinyl nitrogens and phenolic oxygens and the other compartment has two oxime nitrogens and phenolic oxygens as coordinating sites. The complexes were characterized by elemental and spectral analysis. Electrochemical studies of the complexes show two step single electron quasi-reversible redox processes at cathodic potential region. For copper complexes E¹ _pc=−0.18 to −0.62 and E² _pc=−1.18 to −1.25 V, for nickel complexes E¹ _pc=−0.40 to −0.63 and E² _pc=−1.08 to −1.10 V and reduction potentials are sensitive towards the chemical environment around the copper and nickel atoms. The nickel(II) complexes undergo two electrons oxidation. The first one electron oxidation is observed around +0.75 V and the second around +1.13 V. ESR Spectra of the binuclear copper(II) complexes [Cu₂L](ClO₄), [Cu₂L(Cl)], [Cu₂L(NO₃)] shows a broad signal at g=2.1 indicating the presence of coupling between the two copper centers. Copper(II) complexes show a magnetic moment value of μ_eff around 1.59 B.M at 298 K and variable temperature magnetic measurements show a −2J value of 172 cm⁻¹ indicating presence of antiferromagnetic exchange interaction between copper(II) centres.     

Synthesis of new Cu(II), Ni(II) and Co(II) complexes with a bis-amide ligand functionalized with pyridine moieties: Spectral, magnetic and electrochemical studies

Three new copper(II), nickel(II) and cobalt (II) dinuclear complexes with a bis-amide ligand derived from tartaric acid have been prepared and characterized. For this purpose, the ligand (R,R)-(+)-di-N,N′-methylpyridino-tartramide (dmpt) was synthesized via the classical aminolysis of (R,R)-(+)-dimethyltartrate with pyridylmethylamine. The molecular structures of the complexes Na[Cu₂(dmptH₋₃)(CO₃)] · 8H₂O (1) and [Ni₂(dmptH₋₂)₂] · 9.75H₂O (2) were elucidated by X-ray diffraction, and the complex [Co₂(dmptH₋₃)(μ-OH)] · NaClO₄ · 5H₂O (3) by XAS. The crystal structure of (1) shows that the two metallic centres are in a square planar environment. Each copper(II) is bound to pyridyl and deprotonated amidic nitrogen atoms and to the oxygen atoms of hydroxyl and carbonato groups. In complex (2), both nickel atoms are in a distorted octahedral environment with an identical set of donors atoms, N₄O₂, coming from four nitrogen atoms of two pyridylmethylamido moieties and two oxygen donor atoms of alcohol groups. XAS analysis of complex (3) allows us to propose a CoN₂O₄ chromophore, with two nitrogen atoms coming from pyridyl and amidic groups and two bridged oxygen atoms from a deprotonated alcohol group and an hydroxyl group; the hexacoordination is achieved by two water molecules. The spectroscopic, electrochemical and magnetic properties of these complexes were investigated.     

A study of the spectrophotometric determination of traces of cadmium(II) and copper(II) with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol in the presence of polyglycol octylphenyl ether

A spectrophotometric study of the Cd(II) and Cu(II) complex of a new reagent, 2-(5-bromo-2-pyridylazo)-5-diethylamino phenol (5-Br-PADAP) in the presence of polyglycol octylphenyl ether (OP) is presented. A reddish binary complex is formed at pH 9 and shows maximal absorbance at 560 nm with molar absorptivity of 1.16 × 10⁵ · mol⁻¹ · cm⁻¹ liter (Cd), 1.5 × 10⁵ mol⁻¹ · cm⁻¹ · liter (Cu). Beer's law is followed over the range 0.0 to 20 μg cadmium(II) and 0.0–18 μg copper(II). The continuous variation method and molar ratio method showed that the metal ligand ratio is 1:2; ordinarily, most ions do not interfere with the determination and the method can be applied for direct spectrophotometric determination of cadmium(II) and copper(II) in actual samples and the results obtained are satisfactory.     

Spectrophotometric determination of cobalt(II) with 2-(3′-sulfobenzoyl)pyridine benzoylhydrazone

A simple method has been described for the Spectrophotometric determination of cobalt(II) with 2-(3′-sulfobenzoyl)pyridine benzoylhydrazone (SBPBH). In aqueous solution, cobalt(II) reacts with SBPBH to form a yellow complex, which is not destroyed even by the addition of 3.8 M perchloric acid. The absorption maximum of the complex in 1.5 M perchloric acid medium was found to be 400 nm; the molar absorptivity was 2.17 × 10⁴ liters mol⁻¹ cm⁻¹. The proposed method is fairly selective and has been applied to the determination of cobalt in standard alloy steel samples.     

Determination of trace amounts of mercury(II) in water samples using a novel kinetic catalytic ligand substitution reaction of hexacyanoruthenate(II)

A simple, sensitive, selective and rapid kinetic catalytic method has been developed for the determination of Hg(II) ions at micro-level. This method is based on the catalytic effect of Hg(II) ion on the rate of substitution of cyanide in hexacyanoruthenate(II) with nitroso-R-salt (NRS) in aqueous medium and provides good accuracy and precision. The concentration of Hg(II) catalyst varied from 4.0 to 10.0 × 10⁻⁶ M and the progress of reaction was followed spectrophotometrically at 525 nm (λ_max of purple-red complex [Ru(CN)₅NRS]³⁻,  = 3.1 × 10³ M⁻¹ s⁻¹) under the optimized reaction conditions; 8.75 × 10⁻⁵ M [Ru(CN)₆⁴⁻], 3.50 × 10⁻⁴ M [nitroso-R-salt], pH 7.00 ± 0.02, ionic strength, I = 0.1 M (KCl), temp 45.0 ± 0.1 °C. The linear calibration curves, i.e. calibration equations between the absorbance at fixed times (t = 15, 20 and 25 min) versus concentration of Hg(II) ions were established under the optimized experimental conditions. The detection limit was found to be 1.0 × 10⁻⁷ M of Hg(II). The effect of various foreign ions on the proposed method has also been studied and discussed. The method has been applied to the determination of mercury(II) in aqueous solutions.     

Column Preconcentration of Aluminum and Copper(II) in Alloys, Biological Samples, and Environmental Samples with Alizarin Red S and Cetyltrimethylammonium-Perchlorate Adsorbent Supported on Naphthalene Using Spectrometry

A column method has been established for the preconcentration of aluminum and copper(II) with Alizarin Red S and a cetyltrimethylammonium-perchlorate ion pair supported on naphthalene, using a simple glass-tipped tube. Aluminum and copper(II) react with Alizarin Red S to form water-soluble colored chelate anions. These chelate anions form water-insoluble ternary complexes with the adsorbent on the inactive surface of naphthalene packed into a column. They are quantitatively retained in the pH ranges of 4.7-5.2 for aluminum and 5.0-10.0 for copper. The solid mass is dissolved out from the column with 5 ml of dimethylformamide (DMF) for aluminum and 5 ml of ethanol for copper and the absorbance was measured with a spectrometer at 525 nm for aluminum and at 529 nm for copper. The calibration curves were linear over the concentration ranges of 0.25-5.0 μg of aluminum in 5 ml of DMF solution and 0.50-12.0 μg of copper in 5 ml of ethanol solution. The molar absorptivities and Sandell′s sensitivities were respectively calculated to be 2.8 × 10⁴ liter · mol⁻¹ · cm⁻¹ and 9.62 × 10⁻⁴ μg · cm⁻² for aluminum and 2.5 × 10⁴ liter · mol⁻¹ · cm⁻¹ and 2.5 × 10⁻³ μg · cm⁻² for copper. Seven replicate determinations of sample solutions containing 2.5 μg of aluminum and 6.0 μg of copper gave mean absorbances of 0.520 and 0.480 with relative standard deviations of 1.67 and 0.33%, respectively. Interference due to various foreign ions has been studied and the method has been applied to the determination of aluminum in standard alloys, tea leaves, vehicle particulates, copper in coal fly ash, and commercial salt samples.     

Synthesis and vibrational study of platinum(II) and palladium(II) complexes of glyoxilic acid oxime

New platinum(II) and palladium(II) complexes of glyoxilic acid oxime (gao) have been prepared and characterised by infrared (4000–150 cm⁻¹) and Raman (4000–200 cm⁻¹) spectra. The gao acts as bidentate ligand bonding through the oxime nitrogen and carboxyl oxygen atoms to form neutral bis-chelate square-planar complexes. The lowest energy conformer of the gao ligand (ectt) was selected among 16 theoretically possible conformers on the basis of ab initio calculations at HF/3-21G*, HF/6-31G* and HF/6-311** levels of the theory from which structural parameters and conformational stabilities have been obtained. A complete vibrational assignment of the gao was performed for the lowest energy ectt conformer on the basis of ab initio optimised parameters and normal coordinate analysis calculations (PED). NCA calculations of the complexes studied were also performed.     

Voltammetric determination of N-acetylcysteine using a carbon paste electrode modified with copper(II) hexacyanoferrate(III)

The preparation and electrochemical characterization of a carbon paste electrode modified with copper(II) hexacyanoferrate(III) (CuHCF) as well as its behavior as electrocatalyst toward the oxidation of N-acetylcysteine were investigated. The electrochemical behavior of the modified electrode and the electrooxidation of N-acetylcysteine were explored using sweep linear voltammetry. The best voltammetric response was observed for a paste composition of 20% (w/w) copper(II) hexacyanoferrate(III) complex, acetate buffer solution at pH of 6.0 as the electrolyte and scan rate of 10 mV s^− 1. A linear voltammetric response for N-acetylcysteine was obtained in the concentration range from 1.2 × 10^− 4 to 8.3 × 10^− 4 mol L^− 1, with a detection limit of 6.3 × 10^− 5 mol L^− 1. The proposed electrode is useful for the quality control and routine analysis of N-acetylcysteine in pharmaceutical formulations.     

Synthesis and spectroscopic properties of a new bipyridine-bipyrazoyl(pyridine)-thiocyanato-ruthenium(II) complex

The complex [Ru(II)(dcbpyH₂)(bdmpp)NCS](PF₆) (1) (where dcbpyH₂ is 2,2′-bipyridine-4,4′-dicarboxylic acid, bdmpp is 2,6-bis(3,5-dimethyl-N-pyrazoyl)pyridine,) is synthesized and characterized extensively by ¹H NMR and ¹³C NMR 1D and 2D, mass spectroscopy, cyclic voltammetry, electronic absorption spectroscopy and IR. The half-wave potential of the Ru(II)/Ru(III) redox couple was measured at E_1/2=+0.795 V versus Ag/AgCl in CH₃CN. The complex presents three intense metal-to-ligand charge transfer (MLCT) (d_M→π_L*) absorption bands centered at 383 (=21 300 M⁻¹ cm⁻¹), 432 (=22 400 M⁻¹ cm⁻¹) and 475 nm (=23 400 M⁻¹ cm⁻¹), respectively. The absorbance is extremely strong between 400 and 500 nm and even at 620 nm, the extinction coefficient is still high (=3768 M⁻¹ cm⁻¹). The strong π-acceptor property of the trans-isothiocyanate ligand compared with the Cl⁻ ligand is probably the cause of the blue-shift observed in complex 1. These properties make the complex potentially promising for the photosensitization process. The incorporation of TiO₂ photoelectrodes derivatized with this complex into a solar cell using a composite polymer/inorganic oxide solid-state electrolyte confirmed its sensitizing ability. Incident monochromatic photon-to-current conversion efficiency (IPCE) values of about 30% and overall energy conversion efficiency (η) of 1.7% were obtained.     

Studies on mononuclear chelates derived from substituted Schiff-base ligands (part 6): synthesis and characterization of a new 3-ethoxysalicyliden- p -aminoacetophenoneoxime and its complexes with cobalt(II), nickel(II), copper(II) and zinc(II)

Schiff-base complexes of cobalt(II), nickel(II), copper(II) and, zinc(II) with 3-ethoxysalicyliden-p-aminoacetophenoneoxime (HL) were prepared and characterized on the basis of elemental analyses, IR, ¹H- and ¹³C-NMR, electronic spectra, magnetic susceptibility measurements, molar conductivity and thermogravimetric analyses (TGA). A tetrahedral geometry has been assigned to the complexes.     

Spectrophotometric study of Cd(II), Pb(II), Hg(II) and Zn(II) complexes with 5,10,15,20-tetrakis(4-carboxylphenyl)porphyrin

The reaction of 5,10,15,20-tetrakis(4-carboxylphenyl)porphyrin (TCPP) with Cd(II), Pb(II), Hg(II) and Zn(II) was studied spectrophotometrically and kinetics, equilibrium constants as well as photodecomposition of complexes were determined. It was verified that these metal ions with large radius accelerate the incorporation reaction of zinc into TCPP. On the basis of the mechanism and kinetics of this reaction, a sensitive method for the spectrophotometric determination of trace amounts of Zn(II) has been developed. The molar absorptivity of examined Zn-TCPP complex and Sandell's sensitivity at 423 nm were 3.5×10⁵ M⁻¹ cm⁻¹ and 18.3 ng cm⁻². The detection limit for the recommended procedure was 1.4×10⁻⁹ M (0.9 ng ml⁻¹) and precision in range 20-100 ng ml⁻¹ not exceeds 2.7% RSD. The proposed method applied for zinc determination in natural waters and nutritional supplement was compared with AAS results and declared value.     

Kinetic spectrophotometric method for the determination of urinary cobalt based on its catalytic effect on the oxidation of -adrenaline hydrochloride by hydrogen peroxide

A catalytic for determination of nanomolar concentrations of Co(II), i.e., oxidation of -adrenaline hydrochloride with H₂O² in alkaline medium, is proposed. The reaction gives a low limit of detection of 2.5 × 10 ⁻⁹ M Co(II) in the reaction mixture, good reproducibility with a relative standard deviation (R.S.D.) of 4−5% in the Co(II) concentration range 8.0 × 10⁻⁹−8.0 × 10⁻⁸M and good selectivity. On the basis of this indicator reaction, a catalytic-spectrophotometric method for the determination of cobalt in small urine samples (5.00 ml) was elaborated. The analysis of 17 urine samples, taken from healthy persons of different ages, gave cobalt concentrations in the range 0.20–1.50 μmol 1⁻¹. The R.S.D. for ten replicate analyses of a urine sample with an average cobalt content of 0.63 μmol 1⁻¹ was 5.6%. The reliability of the method was verified by a comparative photometric method (r = 0.9755) and by a determination based on known additions of cobalt (r = 0.9894).     

Synthesis,crystal and molecular structure and magnetic properties of an extended two-dimensional fumarato-bridged polymeric cobalt(II) complex [Co(μ-fumarato)(γ-methylpyridine)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>]<Subscript>∞</Subscript>

An extended hydrogen-bonded two-dimensional fumarato-bridged complex [Co(μ-fumarato)(γ-methylpyridine)₂(H₂O)₂]_∞ has been synthesized and its crystal structure determined by single crystal X-ray analysis. The X-ray analysis reveals that the cobalt atom is positioned in distorted octahedral surroundings. An extended twodimensional structure was formed through interchain hydrogen bonding. Magnetic measurements showed the presence of weak antiferromagnetic exchange interactions between the cobalt(II) ions within the chain, based on the spin Hamilitonian H = −2J ∑ S_i S_{i+ 1} (J = − 0.22 cm⁻¹).     

Complexes of heteroscorpionate trispyrazolylborate ligands. Part VI. Carboxylate induced conversion of mono-ligand Tp′M(L) into bis-ligand Tp′2M complexes (M=Co(II) and Cu(II))

A series of homoleptic complexes of hexacoordinate cobalt(II) and copper(II) complexes with 3,5-disubstituted homo- and heteroscorpionate tris(pyrazolyl)borate anionic ligands (Tp′) were synthesized, i.e. bis[hydrotris(3-phenyl,5-methylpyrazol-1-yl)borato]cobalt(II), bis[hydrobis(3-phenyl,5-methylpyrazol-1-yl)(3-methyl,5-phenylpyrazol-1-yl)borato]cobalt(II) and bis[hydrobis(3-phenyl,5-methylpyrazol-1-yl)(3-methyl,5-phenylpyrazol-1-yl)borato]copper(II) and their structures were elucidated crystallographically. The complexes were also formed spontaneously during attempted metathesis of the corresponding Tp′M(NCS) complexes into Tp′M(OOCCH(OH)CH₃) complexes. In the case of the analogous conversion applied for the thiocyanato [hydrobis(3-phenyl,5-methylpyrazol-1-yl)(3,5-dimethylpyrazol-1-yl)boratocobalt(II) complex with sodium carboxylates (lactate, pyruvate and 2-hydroxybutyrate), the cross-transfer of pyrazolyl residues between starting anionic ligands was observed resulting in formation of bis-ligand homo- and heteroleptic Tp′CoTp″ complexes, where Tp′, Tp″ were tris(pyrazolyl)borates composed of n 3(5)-phenyl,5(3)-methylpyrazolyl and (3−n) 3,5-dimethylpyrazolyl residues (n=0–3) identified by mass spectrometry. Metathesis of thiocyanate in thiocyanato hydrotris(3-phenyl,5-methylpyrazol-1-yl)boratocobalt(II) into pyruvate led to the isolation of stable the pyruvato hydrotris(3-phenyl,5-methylpyrazol-1-yl)boratocobalt(II) complex, the structure of which was determined crystallographically. The Tp′ ligands are η³ coordinated to metal ions in every case, whereas the pyruvate anion is coordinated through carboxylate and carbonyl oxygen atoms to the cobalt center. Two rotational isomers distinguishable by ¹H NMR spectroscopy for the hexacoordinate bis[hydrobis(3-phenyl,5-methylpyrazol-1-yl)(3-methyl,5-phenylpyrazol-1-yl)borato]cobalt(II) complex were detected in solution.     

Preparation, characterization and crystal structures of copper(II) hexaazamacrotetracyclic complexes with organic ligands

The reaction of [Cu(L)](ClO₄)₂ · H₂O (L=1,3,10,12,16,19-hexaazatetracyclo[17,3,1,1^12.16,0^4.9]tetracosane) with NaN₃ and Na₂tp yields mononuclear and dinuclear copper(II) complexes, [Cu(L)(N₃)](ClO₄) (1) and [Cu(L)(μ-tp)](ClO₄) · 2H₂O (2). These complexes have been characterized by X-ray crystallography, electronic absorption, cyclic voltammetry and magnetic susceptibility. The crystal structure of (1) shows that the copper(II) ion has a distorted square-pyramidal geometry with the two secondary and two tertiary amines of the macrocycle and one nitrogen atom from the azide group coordinating the axial position. The copper(II) ions in (2) are bridged by the terephthalate anion to form a dinuclear complex, in which each copper(II) ion reveals a distorted square-pyramid with four nitrogen atoms of the macrocycle and the oxygen atom of bridging tp ligand. Cyclic voltammetry of the complexes gives two one-electron waves corresponding to Cu^II/Cu^III and Cu^II/Cu^I processes. The magnetic susceptibility measurement for (2) exhibits a weak antiferromagnetic interaction between copper(II) centers with a 2J value of −2.21 cm⁻¹ (H = −2JΣS₁ · S₂). The electronic spectra and electrochemical behavior of the complexes are significantly affected by the nature of the organic ligands.     

Enhanced sensitivity for Cu(II) by a salicylidine-functionalized polysiloxane carbon paste electrode

A new approach for decreasing the detection limit for a copper(II) ion-selective electrode (ISE) is presented. The ISE is designed using salicylidine-functionalized polysiloxane in carbon paste. This work describes the attempts to develop the electrode and measurements of its characteristics. The new type of renewable three-dimensional chemically modified electrode could be used in a pH range of 2.3–5.4, and its detection limit is 2.7 × 10⁻⁸ mol L⁻¹ (1.2 μg L⁻¹). This sensor exhibits a good Nernstian slope of 29.4 ± 0.5 mV/decade in a wide linear concentration range of 2.3 × 10⁻⁷ to 1.0 × 10⁻³ mol L⁻¹ of Cu(II). It has a short response time (8 s) and noticeably high selectivity over other Cu(II) selective electrodes. Finally, it was satisfactorily used as an indicator electrode in complexometric titration with EDTA and determination of copper(II) in miscellaneous samples such as urine and various water samples.     

Spectrophotometric determination of cobalt as the orange cobalt-biacetylmonoxime 2-pyridylhydrazone complex

A spectrophotometric method for the determination of cobalt is described. The method is based on the formation of an orange color by reaction of cobalt(II) with biacetylmonoxime 2-pyridylhydrazone in basic solutions. The molar absorptivity at 480 nm is about 9.2 × 10³ liters mol⁻¹ cm⁻¹ (pH 10) and spectrophotometric sensitivity is 0.0062 μg Co cm⁻² for ABSORBANCE = 0.001.     

A Potentiometric and Spectroscopic Investigation of Copper(II)– and Zinc(II)–Orotate Complex Equilibria Under Physiological Conditions

A quantitative study of zinc(II) and copper(II) complex formation with orotic acid has been performed under physiological conditions (37°C; 0.15 mol-dm^–3 NaCl) using the glass electrode potentiometric technique. Several species have been identified within the pH range 2–10 for the metal-to-ligand concentration ratios investigated. Three mononuclear complexes, ML, ML₂, and ML₂H_–1, have been characterized with both metals. In addition, the polynuclear species M₃L₂H_–2 has been found with copper(II). Formation constants for all these species have been calculated with the help of the SUPERQUAD computer program. UV absorption and IR spectroscopic measurements combined with speciation calculations have been used to confirm corresponding structures.     

Novel heteroligand complexes of Co(II), Cu(II), Ni(II) and Mn(II) formed by 2,2′-dipyridyl or 1,10-phenanthroline and phosphortriamide ligands: Synthesis and structure

This paper presents examples of mixed-ligand Co(II), Cu(II), Ni(II) and Mn(II) complexes, with a distorted octahedral coordination geometry, with 2,2′-dipyridyl or 1,10-phenanthroline and phosphortriamide ligands. The complexes of the general type ML₂·Lig (where M = Co(II), Cu(II), Ni(II), Mn(II); L⁻ = {Cl₃C(O)NP(O)R₂}⁻ (R = NHBz, NHCH₂CHCH₂, NEt₂); Lig = 2,2′-dipyridyl or 1,10-phenanthroline) were synthesised and characterised by means of X-ray diffraction, IR and UV–Vis spectroscopy. The phosphortriamide ligands are coordinated via oxygen atoms of phosphoryl and carbonyl groups involved in six-membered metal cycles. The additional ligands 2,2′-dipyridyl or 1,10-phenanthroline are coordinated to the central atom, forming five-membered cycles.     

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, [Ni₃(salpen)₂(OAc)₂(H₂O)₂]·4H₂O (1) (OAc = acetate, CH₃COO⁻), [Ni₃(salpen)₂(OBz)₂] (2) (OBz = benzoate, PhCOO⁻) and [Ni₃(salpen)₂(OCn)₂(CH₃CN)₂] (4) (OCn = cinnamate, PhCHCHCOO⁻), H₂salpen = 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, [Ni₃(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.