The syntheses and magnetic properties of a series of heterospin [LnIIICuII 4] pentanuclear complexes

Twelve oxamide-bridged Ln(III)–Cu(II) heteropentanuclear complexes Ln[Cu(PMoxd)]₄(ClO₄)₃ · 5H₂O (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, and PMoxd = the N,N′-Bi(α-pyridylmethyl)-oxamide dianion) and 12 oxamide-bridged Ln(III)–Cu(II) heteropentanuclear complexes with the formula of Ln[Cu(PEoxd)]₄(ClO₄)₃ · 5H₂O (PEoxd = the N,N′-Bi(α-pyridylethyl)-oxamide dianion) were synthesized and characterized. The magnetic properties of Gd[Cu(PMoxd)]₄(ClO₄)₃ · 5H₂O (7) and Gd[Cu(PEoxd)]₄(ClO₄)₃ · 2H₂O (19) show that there are ferromagnetic interactions between Gd(III) and Cu(II) in the complexes with J _Cu–Gd = 1.38 cm^?1 and J _Cu–Gd = 1.00 cm^?1, respectively. Fluorescent quenching phenomena for Eu[Cu(PMoxd)]₄(ClO₄)₃ · 5H₂O (6) and Tb[Cu(PMoxd)]₄(ClO₄)₃ · 5H₂O (8) were also observed.     

Structures and magnetic properties of two new heterospin complexes involving nitroxide radicals and oxamido-bridged copper(II)

Two new binuclear copper(II) complexes containing four spin carriers with pyridyl-substituted nitroxide radicals have been synthesized and characterized structurally and magnetically. These complexes are formulated as [Cu₂(oxap)(IM4py)₂](ClO₄)₂ (1) and [Cu₂(oxap)(NIT4py)₂](ClO₄)₂ (2), respectively, in which oxap stands for N,N′-bis(2-aminopropyl). IM4py stands for 2-(4′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl and NIT4py for 2-(4′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide. The structures of the complexes consist of centro-symmetric trans oxamido-bridged copper(II) binuclear units and nitroxide radicals. In 1 and 2 the copper atoms are in a distorted square plane and radicals (IM4py and NIT4py) coordinate to copper via nitrogen atoms from pyridine rings. Magnetic analysis indicates that 1 and 2 exhibit strong metal-metal antiferromagnetic coupling through oxamido-bridged and antiferromagnetic exchange interactions between copper(II) ion and radicals, respectively. The magnetic behaviors are discussed with reference to their crystal structures.     

Synthesis, structure, and magnetic properties of (6-9)-nuclear Ni(II) trimethylacetates and their heterospin complexes with nitroxides

New polynuclear nickel trimethylacetates [Ni6(OH)4(C5H9O2)8(C5H10O2)4] (6), [Ni7(OH)7(C5H9O2)7(C5H10O2)6(H2O)] x 0.5 C6H14 x 0.5 H2O (7), [Ni8(OH)4(H2O)2(C5H9O2)12] (8), and [Ni9(OH)6(C5H9O2)12(C5H10O2)4] x C5H10O2 x 3 H2O (9), where C5H9O2 is trimethylacetate and C5H10O2 is trimethylacetic acid, have been found. Their structures were determined by X-ray crystallography. Because of their high solubility in low-polarity organic solvents, compounds 6-9 reacted with stable organic radicals to form the first heterospin compounds based on polynuclear Ni(II) trimethylacetate and nitronyl nitroxides containing pyrazole (L(1)-L(3)), methyl (L(4)), or imidazole (L(5)) substituent groups, respectively, in side chain [Ni7(OH)5(C5H9O2)9(C5H10O2)2(L(1))2(H2O)] x 0.5 C6H14 x H2O (6+1a), [Ni7(OH)5(C5H9O2)9(C5H10O2)2(L2)2(H2O)] x H2O (6+1b), [Ni7(OH)5(C5H9O2)9(C5H10O2)2(L(3))2(H2O)] x H2O (6+1c), [Ni6(OH)3(C5H9O2)9(C5H10O2)4(L(4))] x 1.5 C6H14 (6'), and [Ni4OH)3(C5H9O2)5(C5H10O2)4(L(5))] x 1.5 C7H8 (4). Their structures were also determined by X-ray crystallography. Although Ni(II) trimethylacetates may have varying nuclearity and can change their nuclearity during recrystallization or interactions with nitroxides, this family of compounds is easy to study because of its topological relationship. For any of these complexes, the polynuclear framework may be derived from the [Ni6] polynuclear fragment {Ni6(mu4-OH)2(mu3-OH)2(mu2-C5H9O2-O,O')6(mu2-C5H9O2-O,O)(mu4-C5H9O2-O,O,O',O')(C5H10O2)4}, which is shaped like an open book. On the basis of this fragment, the structure of 7-nuclear compounds (7 and 6+1a-c) is conveniently represented as the result of symmetric addition of other mononuclear fragments to the four Ni(II) ions lying at the vertexes of the [Ni6] open book. The 9-nuclear complex is formed by the addition of trinuclear fragments to two Ni(II) ions lying on one of the lateral edges of the [Ni6] open book. This wing of the 9-nuclear complex preserves its structure in another type of 6-nuclear complex (6') with the boat configuration. If, however, two edge-sharing Ni(II) ions are removed from [Ni6] (one of these lies at a vertex of the open book and the other, on the book-cover line), we obtain a 4-nuclear fragment recorded in the molecular structure of 4. Twinning of this 4-nuclear fragment forms highly symmetric molecule 8, which is a new chemical version of cubane.     

New types of heterospin complexes from trans-oxamido-bridged copper(II) binuclear units and nitronyl nitroxide radicals: crystal structure and magnetic characterization

Three new heterospin complexes derived from trans-oxamido-bridged copper(II) binuclear units [Cu(2)(oxen), oxen = N,N-bis(2-aminoethyl)oxamide] and pyridine-substituted nitronyl nitroxides (o-, m-, and p-PYNN) were synthesized and characterized structurally and magnetically. Complexes 1 and 2 are four-spin complexes. Interestingly, it is found that in complex 3, the Cu(II) ions and m-PYNN units are arranged to form 1D double-stranded helical chains, which to the best of our knowledge is the first example of a metal nitronyl nitroxide complex with such a 1D helical structure. The temperature dependencies of the magnetic susceptibilities of 1 and 2 were fitted to the four-spin model with the Hamiltonian H = -2Js(Cu1)s(Cu2) - 2j(s(Cu1)s(rad1) - s(Cu2)s(rad2)), leading to J = -150.5 cm(-)(1) and j = 47.2 cm(-)(1) for complex 1 and J = -191.7 cm(-)(1) and j = -18.9 cm(-)(1) for complex 2. The temperature dependence of the magnetic susceptibility of complex 3 was approximately simulated with a simple model composed of a dimer of Cu(II) ions and two m-PYNN molecules. The best fitting leads to the values of J = -183.0 cm(-)(1) and zJ' = -0.55 cm(-)(1) for the magnetic exchange of two Cu(II) ions through the oxamide bridge and that between the dimer of Cu(II) ions and two m-PYNN molecules, respectively. The antiferromagnetic exchange of oxamido-bridged Cu(II) ions in complexes 1-3 is strong. The strength of such antiferromagnetic interactions is also similar for the three complexes.     

Synthesis,structure, and magnetic properties of heterotrimetallic tetranuclear complexes

Two novel heterotrimetallic tetranuclear complexes [Cu(H₂L)(CH₃OH)]₂Gd(DMF)Fe(CN)₆·2H₂O·DMF (1) and [Cu(H₂L)(CH₃OH)]₂Tb(H₂O)_0.57(DMF)_0.43Fe(CN)₆·5.5H₂O (2) are reported (H₄L = N,N′-ethylenebis(3-hydroxysalicylidene)). The central Ln(III) ion is surrounded by two neutral [Cu(H₂L)(CH₃OH)] moieties, forming a Cu₂Ln trinuclear unit. The [Fe(CN)₆]^3? anion is weakly coordinated to one Cu(II) ion of [Cu(H₂L)(CH₃OH)] through a cyanide nitrogen atom with the N–Cu distance of ca. 3.2 Å. Magnetic susceptibility measurements indicate the presence of overall ferromagnetic interactions in complexes 1 and 2. The magnetic coupling constant in complex 1 is J _Cu1Gd1 = 4.54 cm^?1 and J _Cu2Gd1 = 7.97 cm^?1 based on \( \hat{H} = - 2J_{\text{Cu1Gd1}} \hat{S}_{\text{Cu1Gd1}} - 2J_{\text{Cu2Gd1}} \hat{S}_{\text{Cu2Gd1}} \) . Dynamic AC magnetic susceptibility studies reveal that complex 2 shows frequency-dependent out-of-phase signals, typical of single molecule magnet behavior. The energy barrier for complex 2 under a 2 kOe applied DC magnetic field is 13 K.     

Crystal structure of mixed-ligand complexes of the Ni(II) heterospin bischelate withiso-butyl alcohol and 1,4-Butanediol

The crystal structures of the mixed-ligand complexes of the heterospin bischelate bis [2,2,5,5-tetramethyl-l-oxyl-3-imidazoline-4-(3’,3’,3’-trifluoro-1’-propenyl-2’-oxiato)nickel(II) (NiL₂) with iso-butanol and 1,4-butanediol NiL₂(i-C₄H₉OH)₂ and NiL₂[HO(CH₂)₄OH], respectively, are determined. The crystal structure of the NiL₂ complex with the normal butyl alcohol NiL₂(n-C₄H₉OH)₂ and the structure of CoL₂[HO(CH₂)₄OH] are refined. Translated fromZhurnal Strukturnoi Khimii, Vol. 38, No. 5, pp. 930–945, September-October, 1997.     

Effect of the high pressure on the structure and intercalation properties of lithium-nickel-manganese oxides

Lithium-nickel-manganese oxides (Li_1+x(Ni_1/2Mn_1/2)_1−xO₂, x=0 and 0.2), having different cationic distributions and an oxidation state of Ni varying from 2+ to 3+, were formed under a high-pressure (3 GPa). The structure and cationic distribution in these oxides were examined by powder X-ray diffraction, infrared (IR) and electron paramagnetic resonance (EPR) in X-band (9.23 GHz) and at higher frequencies (95 and 285 GHz). Under a high pressure, a solid-state reaction between NiMnO₃ and Li₂O yields LiNi_0.5Mn_0.5O₂ with a disordered rock-salt type structure. The paramagnetic ions stabilized in this oxide are mainly Ni²⁺ and Mn⁴⁺ together with Mn³⁺ (about 10%). The replacement of Li₂O by Li₂O₂ permits increasing the oxidation state of Ni ions in lithium-nickel-manganese oxides. The higher oxidation state of Ni ions favours the stabilization of the layered modification, where the Ni-to-Mn ratio is preserved: Li(Li_0.2Ni_0.4Mn_0.4)O₂. The paramagnetic ions stabilized in the layered oxide are mainly Ni³⁺ and Mn⁴⁺ ions. The disordered and ordered phases display different intercalation properties in respect of lithium. The changes in local Ni,Mn-environment during the electrochemical reaction are discussed on the basis of EPR and IR spectroscopy.     

Crystal structure and magnetic properties of dicarboxylate-bridged linear chain Mn(II) complexes

Two manganese(II) complexes, [Mn(mtm)(CH₃OH)₂(H₂O)]_n (1) and [Mn₂(mtm)₂(2,2′-bipy)₂]_n (2) (bipy=bipyridine, mtm=[bis(methylthio)methylene]malonate) were synthesized and characterized by X-ray crystallography. Structure of 1 consists of octahedral manganese(II) species which are extended by carboxylate bridges in syn–anti fashion along the c-axis. Chains of 1 are associated by hydrogen bonding among coordinating water and methanol molecules and carboxylate oxygen atoms, forming two-dimensional structures. The crystallographic asymmetric unit of 2 comprises two [Mn(2,2′-bipy)(mtm)] units in which Mn(II) atoms are bridged by μ₂-oxygens from carboxylate to form Mn₂O₂ rhombus. The dimeric units are linked doubly by second carboxylates in syn–anti fashion, resulting in a chain structure. The antiferromagnetic coupling of Mn(II) ions in 1 (−0.2 cm⁻¹) and 2 (−1.57 cm⁻¹) was determined from variable-temperature magnetic susceptibility data in the temperature range of 2–300 K.     

Effect of stoichiometry and pH on the structure and properties of Chitosan/Chondroitin sulfate complexes

This work reports the formation of chitosan (CHT)/chondroitin sulfate (CS) polyelectrolyte complexes and evaluates the changes in their complexation-stoichiometries, crystallinity, and mechanical properties at different pHs used for both complex preparation and swelling. Through high-performance liquid chromatography, the changes in CHT/CS complex stoichiometry due to CS release from CHT/CS complexes, which occurred mainly during swelling at pH ??6, were determined. In addition, strong evidences of self-assembling on CHT/CS complex network as swelled at pH?12 buffer were observed by WAXS patterns. Such a new rearrangement of the network increases the CHT/CS complexes rigidity as well as their elastic moduli, E, as observed through compressive tests. The results found in this work provide new information to allow the tailoring of the biofunctionalities of the CHT/CS complex for the development of physiological pH-compatible materials.     

Effect of high pressure treatment on structure and properties of cellulose in eucalypt pulps

Bleached acid sulphite and kraft Eucalyptus globulus pulps were subjected to treatment at high hydrostatic pressure (400 MPa during 10 min). The associated structural changes of cellulose were evaluated by X-ray scattering, solid-state NMR and infrared spectroscopy. The high pressure treatment promoted the growth of crystalline domains predominantly via lateral aggregation (cocrystallization) and, to some extent, due to the accretion of cellulose from noncrystalline domains (recrystallization). The treated pulps exhibited increment of the amount of strongly bound water and improved accessibility to amorphous domains. The high pressure treatment of dried sulphite pulp led to restoration, at least partially, of its swelling capacity thus diminishing the hornification features. Pressure treated dried sulphite pulp showed improved fibre bonding capacity at simultaneously increased bulk of the produced handsheets. The results obtained clearly showed the potential of high pressure treatments for the modification of cellulosic fibres in different applications.     

Effect of polyol structure on the properties of the resultant magnetic polyurethane elastomer nanocomposites

In this study, two types of magnetic polyurethane (PU) elastomer nanocomposites using polycaprolactone (PCL) and polytetramethylene glycol (PTMG) as polyols were synthesized by incorporating thiodiglycolic acid surface modified Fe₃O₄ nanoparticles (TSM‐Fe₃O₄) into PU matrices through in situ polymerization method. TSM‐Fe₃O₄ nanoparticles were prepared using in situ coprecipitation method in alkali media and were characterized by X‐ray diffraction, Fourier Transform Infrared Spectrophotometer, Transmission Electron Microscopy, and Vibrating Sample Magnetometer. The effects of PCL and PTMG polyols on the properties of the resultant PUs were studied. The morphology and dispersion of the nanoparticles in the magnetic nanocomposites were studied by Scanning Electron Microscope. It was observed that dispersion of nanoparticles in PTMG‐based magnetic nanocomposite was better than PCL‐based magnetic nanocomposite. Furthermore, the effect of polyol structure on thermal and mechanical properties of nanocomposite was investigated by Thermogravimetric Analysis and Dynamic Mechanical Thermal Analysis. A decrease in the thermal stability of magnetic nanocomposites was found compared to pure PUs. Furthermore, DMTA results showed that increase in glass transition temperature of PTMG‐based magnetic nanocomposite is higher than PCL‐based magnetic nanocomposite, which is attributed to better dispersion of TSM‐Fe₃O₄ nanoparticles in PTMG‐based PU matrix. Additionally, magnetic nanocomposites exhibited a lower level of hydrophilicity compared to pure PUs. These observations were attributed to the hydrophobic behavior of TSM‐Fe₃O₄ nanoparticles. Moreover, study of fibroblast cells interaction with magnetic nanocomposites showed that the products can be a good candidate for biomedical application. Copyright © 2013 John Wiley & Sons, Ltd.     

Effect of the nature of non-bridging donor atoms on the structure and magnetic properties of binuclear copper(II) complexes with heterocyclic azomethyne ligands

Journal of Structural Chemistry - Pyrazolate bridging binuclear copper(II) complex with a heterocyclic azomethyne ligand (a condensation product of 1,3-diaminopropanol-2 with...     

Crystal structure and magnetic properties of two isomeric three-dimensional pyromellitate-containing cobalt(II) complexes

The hydrothermal preparation, crystal structure determination, and magnetic study of two isomers made up of 1,2,4,5-benzenetetracarboxylate and high-spin Co(II) ions of formula [Co2(bta)(H2O)4]n x 2n H2O (1 and 2; H4bta = 1,2,4,5-benzenetetracarboxylic acid) are reported. 1 and 2 are three-dimensional compounds whose structures can be described as (4,4) rectangular layers of trans-diaquacobalt(II) units with the bta(4-) anion acting as tetrakis-monodentate ligand through the four carboxylate groups, which are further connected through other trans-[Co(H2O)2](2+) (1) and planar [Co(H2O)4](2+) (2) entities, with the bridging units being a carboxylate group in either the anti-syn (1) or syn-syn (2) conformations and a water molecule (2). The study of the magnetic properties of 1 and 2 in the temperature range 1.9-300 K shows the occurrence of weak antiferromagnetic interactions between the high-spin Co(II) ions, with the strong decrease of chi(M)T upon cooling being mainly due to the depopulation of the higher energy Kramers doublets of the six-coordinated Co(II) ions. The computed values of the exchange coupling between the Co(II) ions across anti-syn carboxylate (1) and syn-syn carboxylate/water (2) bridges are J = -0.060 (1) and -1.90 (2) cm(-1) (with the Hamiltonian being defined as H = -Jsigma(i,j)S(i) x S(j)). These values follow the different conformations of the carboxylate bridge in 1 (anti-syn) and 2 (syn-syn) with the occurrence of a double bridge in 2 (water/carboxylate).     

Spirocyclic derivatives of nitronyl nitroxides in the design of heterospin CuII complexes manifesting spin transitions

A method was developed for the synthesis of a nitronyl nitroxide containing cyclopentane substituents in positions 4 and 5 of the imidazoline ring, viz., 2-(3-pyridyl)-4,5-bis(spiropentyl)-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (L^CP). The reaction of Cu^II hexafluoroacetylacetonate with L^CP affords different products depending on the reaction conditions: mononuclear [Cu(hfac)₂(L^CP)₂], binuclear [Cu(hfac)₂L^CP]₂, tetranuclear {[Cu(hfac)₂]₄(L^CP)₂}, or chain polymer {[Cu(hfac)₂]₃(L^CP)₂} _n . Temperature changes induce structural transformations accompanied by a change in the spin state in exchange clusters in the solid [Cu(hfac)₂L^CP]₂ and {[Cu(hfac)₂]₄(L^CP)₂}.     

New tetranuclear Cu(II) complexes: synthesis, structure, and magnetic properties

The synthesis, structure, and magnetic properties of two new tetranuclear Cu(II) complexes containing N,N,N',N'-tetraethylpyridine-2,6-dithiocarboxamide (S-dept) of formula [Cu(2)Cl(2)(mu-S-dept)(2)][Cu(2)Cl(4)(mu-Cl)(2)] (1) and [Cu(2)(mu-Cl)(2)(S-dept)(2)][CuCl(3)(EtOH)](2) (2) are reported. Their X-ray crystal structures reveal that the complexes are composed of anionic and cationic dimers, that in both cases contain the metal centers which interact via Coulombic and/or hydrogen bonding interactions. In both cases, the Cu centers in the anionic moieties adopt a slightly distorted tetrahedral geometry whereas for the cationic moieties they adopt a square-pyramidal type of geometry. Magnetic susceptibility data show that compounds 1 and 2 present an overall antiferromagnetic behavior arising from the contribution of both anionic and cationic moieties. For 1, the best fit obtained gave J(1) = -2.62 +/- 0.19 cm(-1), J(2) = -19.54 +/- 0.47 cm(-1), and g(2) = 2.164 +/- 0.004 cm(-1) (R = 8.28 x 10(-5)) whereas for 2 it gave J(1) = 4.48 +/- 2.73 cm(-1), g(1) = 2.20 +/- 0.03, J(2) = -11.26 +/- 2.01 cm(-1), and g(2) = 2.10 +/- 0.03 (R = 1.15 x 10(-4)). The nature of the superexchange pathways in 1 and 2 is discussed on the basis of structural, magnetic, and molecular orbital considerations. Theoretical calculations are performed at the extended Huckel level in order to obtain their molecular orbitals and energies using their crystallographic data.     

Vapochromic ionic liquids from metal-chelate complexes exhibiting reversible changes in color, thermal, and magnetic properties

Vapor- and gas-responsive ionic liquids (ILs) comprised of cationic metal-chelate complexes and bis(trifluoromethanesulfonyl)imide (Tf(2) N) have been prepared, namely, [Cu(acac)(BuMe(3) en)][Tf(2) N] (1?a), [Cu(Bu-acac)(BuMe(3) en)][Tf(2) N] (1?b), [Cu(C(12) -acac)(Me(4) en)][Tf(2) N] (1?c), [Cu(acac)(Me(4) en)][Tf(2) N] (1?d), and [Ni(acac)(BuMe(3) en)][Tf(2) N] (2?a) (acac=acetylacetonate, Bu-acac=3-butyl-2,4-pentanedionate, C(12) -acac=3-dodecyl-2,4-pentanedionate, BuMe(3) en=N-butyl-N,N',N'-tetramethylethylenediamine, and Me(4) en=N,N,N',N'-trimethylethylenediamine). These ILs exhibited reversible changes in color, thermal properties, and magnetic properties in response to organic vapors and gases. The Cu(II) -containing ILs are purple and turn blue-purple to green when exposed to organic vapors, such as acetonitrile, methanol, and DMSO, or ammonia gas. The color change is based on the coordination of the vapor molecules to the cation, and the resultant colors depend on the coordination strength (donor number, DN) of the vapor molecules. The vapor absorption caused changes in the melting points and viscosities, leading to alteration in the phase behaviors. The IL with a long alkyl chain (1?d) transitioned from a purple solid to a brown liquid at its melting point. The Ni(II) -containing IL (2?a) is a dark red diamagnetic liquid, which turned into a green paramagnetic liquid by absorbing vapors with high DN. Based on the equilibrium shift from four- to six-coordinated species, the liquid exhibited thermochromism and temperature-dependent magnetic susceptibility after absorbing methanol.     

Magnetic behaviors of heterospin chains consisting of cobalt(II) complexes and dipyridylcarbenes

The 1:1 mixture of Co(Brhfpip)(2) and D1py(2) gave isomeric diazocobalt complexes, 1 and 2, formulated by [Co(Brhfpip)(2)(D1py(2))](n). Complexes 1 and 2 have zigzag and linear chain structures by the cis and trans coordination of pyridine units in D1py(2), respectively. After irradiation of microcrystalline samples, the generated carbene interacted with the cobalt ion to form ferromagnetic chains, 1c and 2c. Those isomeric chains exhibited slow magnetic relaxation with U(eff) = 93 and 87 K and H(c) = 20 and 13 kOe at 1.9 K for 1c and 2c, respectively.     

Computational modeling of structure and magnetic properties of dinuclear di-o-benzoquinone iron complexes with linear polycyclic linkers

Density functional theory (DFT UTPSSh/6-311++G(d,p)) quantum chemical modeling of geometry, energy and magnetic characteristics of binuclear iron complexes, in which iron atoms coordinated by 2,11-diaza[3.3](2,6)pyridinophane bases are connected by di-o-benzoquinone ligands with acene linkers, was performed. It is established that the energy diff erence between electromeric forms of the studied compounds is determined by the type of the alkyl substituents at the nitrogen atoms of the tetraazamacrocyclic ligand and does not depend on the structure of the polycyclic chain. The possibility of controlling magnetic properties of the molecules of this type by means of external influences is predicted based on the facts that terminal metal-containing fragments are capable of undergoing thermally induced spin-state switching rearrangements, while the singlet-triplet transition of the acene linker can be induced by light irradiation.

     

Crystal structure and magnetic properties of the octahedral complexes of Ni(II) with 3-imidazoline nitroxides

This paper reports on our studies of the crystal structures and magnetic properties of five mixed-ligand octahedral complexes of Ni(II) with 3-imidazoline nitroxides Ni(RL)₂X₂, where RL are deprotonated enaminoketone derivatives of 3-imidazoline nitroxide with different substituents R (CF₃, Ph) in the side chain, and X is pyridine, dimethylsulfoxide, or semi-phenanthroline. It is established that this type of heterospin system is characterized by an intramolecular exchange interaction parameter (J) of an order of 10 cm⁻¹. Substitution of the N-donor diamagnetic pyridine or phenanthroline by the O-donor dimethylsulfoxide in the coordination sphere of the metal decreases J by 2–3 cm⁻³. A transition from trans-to cis-coordination of the enaminoketone ligands and variation of the R substituent in the chelate ring do not affect the value of J. Deceased. Translated fromZhurnal Struktumoi Khimii, Vol. 39, No. 5, pp. 901–916, September–October, 1998. This work was supported by INTAS grant No. 94-3508 and RFFR grants No. 96-03-33738 and 96-03-32229.