Diamagnetic Ligands Research Articles

Ab initio-based determination of lanthanoid-radical exchange as visualised by inelastic neutron scattering.

Magnetic exchange coupling can modulate the slow magnetic relaxation in single-molecule magnets. Despite this, elucidation of exchange coupling remains a significant challenge for the lanthanoid(iii) ions, both experimentally and computationally. In this work, the crystal field splitting and 4f-π exchange coupling in the erbium-semiquinonate complex [ErTp2dbsq] (Er-dbsq; Tp- = hydro-tris(1-pyrazolyl)borate, dbsqH2 = 3,5-di-tert-butyl-1,2-semiquinone) have been determined by inelastic neutron scattering (INS), magnetometry, and CASSCF-SO ab initio calculations. A related complex with a diamagnetic ligand, [ErTp2trop] (Er-trop; tropH = tropolone), has been used as a model for the crystal field splitting in the absence of coupling. Magnetic and INS data indicate antiferromagnetic exchange for Er-dbsq with a coupling constant of Jex = -0.23 meV (-1.8 cm-1) (-2Jex formalism) and good agreement is found between theory and experiment, with the low energy magnetic and spectroscopic properties well modelled. Most notable is the ability of the ab initio modelling to reproduce the signature of interference between localised 4f states and delocalised π-radical states that is evident in the Q-dependence of the exchange excitation. This work highlights the power of combining INS with EPR and magnetometry for determination of ground state properties, as well as the enhanced capability of CASSCF-SO ab initio calculations and purposely developed ab initio-based theoretical models. We deliver an unprecedentedly detailed representation of the entangled character of 4f-π exchange states, which is obtained via an accurate image of the spin-orbital transition density between the 4f-π exchange coupled wavefunctions.

Magnetism of single-doped paramagnetic tin clusters studied using temperature-dependent Stern-Gerlach experiments with enhanced sensitivity: impact of the diamagnetic ligand field and paramagnetic dopant.

In this work, the magnetic properties of tetrel clusters SnNTM, which are singly doped with transition metals (TM), are investigated. On the one hand, the number of tetrel atoms (N = 11, 12, 14 and 17 with TM = Mn) is varied; on the other hand, different transition metals (N = 14, TM = Cr, Mn, Fe) are studied. Magnetic deflection experiments under cryogenic conditions show that the variation of the number of tetrel atoms strongly changes the magnetic properties of the Mn-doped clusters. It is observed that Sn12Mn, Sn11Mn and Sn14Mn partially show super-atomic behaviour, while spin relaxation occurs in Sn17Mn. Magnetic deflection experiments at higher nozzle temperatures were carried out for the first time enhanced by a second parallel-aligned Stern-Gerlach magnet to achieve larger deflections. The resulting temperature-dependent one-sided deflections are quantitatively analysed using Curie's law and show that Sn17Mn possesses the highest magnetic moment of these clusters, followed by Sn12Mn and Sn11Mn. Sn14Mn shows the lowest magnetic moment. The replacement of Mn by Cr in Sn14Mn leads to a diamagnetic singlet, i.e., the magnetic moment of Cr in Sn14Cr is completely quenched. The replacement of Mn by Fe in turn leads to a paramagnetic species, whereby Sn14Fe is most likely present as a triplet. On this basis, the geometrical and electronic structures are analysed using quantum chemical calculations, indicating an arachno-type structure for Sn14Cr, Sn14Mn and Sn14Fe, which has already been predicted in the literature for Si14Cr. This is experimentally confirmed by deflection of molecular beams with an electric field under cryogenic conditions, suggesting that the arachno-type geometry is crucial for the overall stability of the transition-metal-doped tetrel clusters Sn14TM with TM = Cr, Mn, Fe.

Origin of Weak Magnetic Coupling in a Dimanganese(II) Complex Bridged by the Tetrathiafulvalene-Tetrathiolate Radical.

Magnetic exchange coupling (J) between different spin centers plays a crucial role in molecule-based magnetic materials. Direct exchange coupling between an organic radical and a metal is frequently stronger than superexchange through diamagnetic ligands, and the strategy of using organic radicals to engender desirable magnetic properties has been an area of active investigation. Despite significant advances and exciting bulk properties, the magnitude of J for radical linkers bridging paramagnetic centers is still difficult to rationally predict. It is thus important to elucidate the features of organic radicals that govern this parameter. Here, we measure J for the tetrathiafulvalene-tetrathiolate radical (TTFtt3-•) in a dinuclear Mn(II) complex. Magnetometry studies show that the antiferromagnetic coupling in this complex is much weaker than that in related Mn(II)-radical compounds, in contrast to what might be expected for the S-based chelating donor atoms of TTFtt. Experimental and computational analyses suggest that this small J coupling may be attributed to poor overlap between Mn- and TTFtt-based magnetic orbitals coupled with insignificant spin density on the coordinating S-atoms. These factors override any expected increase in J from the comparatively strong S-donors. This work elucidates the magnetic coupling properties of the TTFtt3-• radical for the first time and also demonstrates how multiple competing factors must be considered in rationally designing organic radical ligands for molecular-based magnetic compounds.

The Microscopic Mechanisms Involved in Superexchange

In earlier work, we previously established a formalism that allows to express the exchange energy J vs. fundamental molecular integrals without crystal field, for a fragment A–X–B, where A and B are 3d1 ions and X is a closed-shell diamagnetic ligand. In this article, we recall this formalism and give a physical interpretation: we may rigorously predict the ferromagnetic (J < 0) or antiferromagnetic (J > 0) character of the isotropic (Heisenberg) spin-spin exchange coupling. We generalize our results to ndm ions (3 ≤ n ≤ 5, 1 ≤ m ≤ 10). By introducing a crystal field we show that, starting from an isotropic (Heisenberg) exchange coupling when there is no crystal field, the appearance of a crystal field induces an anisotropy of exchange coupling, thus leading to a z-z (Ising-like) coupling or a x-y one. Finally, we discuss the effects of a weak crystal field magnitude (3d ions) compared to a stronger (4d ions) and even stronger one (5d ions). In the last step, we are then able to write the corresponding Hamiltonian exchange as a spin-spin one.

Magnetization Dynamics on Isotope-Isomorphic Holmium Single-Molecule Magnets.

Here we reported the deuteration of the metal-binding equatorial water molecules in a reported HoIII single-molecule magnet (SMM) with pentagonal-bipyramidal geometry, from [Ho(CyPh2 PO)2 (H2 O)5 ]3+ to [Ho(CyPh2 PO)2 (D2 O)5 ]3+ . The hyperfine structures originating from the nuclear spin of 165 HoIII can be clearly observed. Moreover, the resulting magnetization dynamics revealed the switch of the relative relaxation rates for the two isotope-isomorphic complexes-respectively faster/slower at low/high temperature. The noticeable isotope effect arises from not only the paramagnetic metal center but also the diamagnetic ligands, which can be explained by the ab initio calculated tunnel splitting and the involvement of the super-hyperfine interaction related to the difference in the nuclear spin number of protium (1 H, I=1 /2 ) and deuterium (2 H, I=1).

Magnetization Dynamics on Isotope‐Isomorphic Holmium Single‐Molecule Magnets

AbstractHere we reported the deuteration of the metal‐binding equatorial water molecules in a reported HoIII single‐molecule magnet (SMM) with pentagonal‐bipyramidal geometry, from [Ho(CyPh2PO)2(H2O)5]3+ to [Ho(CyPh2PO)2(D2O)5]3+. The hyperfine structures originating from the nuclear spin of 165HoIII can be clearly observed. Moreover, the resulting magnetization dynamics revealed the switch of the relative relaxation rates for the two isotope‐isomorphic complexes—respectively faster/slower at low/high temperature. The noticeable isotope effect arises from not only the paramagnetic metal center but also the diamagnetic ligands, which can be explained by the ab initio calculated tunnel splitting and the involvement of the super‐hyperfine interaction related to the difference in the nuclear spin number of protium (1H, I=1/2) and deuterium (2H, I=1).

Copper(II) Pyridyl Aminophenolates: Hypoxia-Selective, Nucleus-Targeting Cytotoxins, and Magnetic Resonance Probes.

Targeting the low-oxygen (hypoxic) environments found in many tumours by using redox-active metal complexes is a strategy that can enhance efficacy and reduce the side effects of chemotherapies. We have developed a series of CuII complexes with tridentate pyridine aminophenolate-based ligands for preferential activation in the reduction window provided by hypoxic tissues. Furthermore, ligand functionalization with a pendant CF3 group provides a 19 F spectroscopic handle for magnetic-resonance studies of redox processes at the metal centre and behaviour in cellular environments. The phenol group in the ligand backbone was substituted at the para position with H, Cl, and NO2 to modulate the reduction potential of the CuII centre, giving a range of values below the window expected for hypoxic tissues. The NO2 -substituted complex, which has the highest reduction potential, showed enhanced cytotoxic selectivity towards HeLa cells grown under hypoxic conditions. Cell death occurs by apoptosis, as determined by analysis of the cell morphology. A combination of 19 F NMR and ICP-OES indicates localization of the NO2 complex in HeLa cell nuclei and increased cellular accumulation under hypoxia. This correlates with DNA nuclease activity being the likely origin of cytotoxic activity, as demonstrated by cleavage of DNA plasmids in the presence of the CuII nitro complex and a reducing agent. Selective detection of the paramagnetic CuII complexes and their diamagnetic ligands by 19 F MRI suggests hypoxia-targeting theranostic applications by redox activation.

Multifrequency Nuclear Magnetic Resonance as an Efficient Tool To Investigate Heterospin Complexes in Solutions.

We report a multifrequency nuclear magnetic resonance (NMR) study of heterospin complexes [Eu(SQ)3Ln], where SQ is 3,6-di(tert-butyl)-1,2-semiquinone, L is tetrahydrofuran (THF), pyridine (Py), or 2,2'-dipyridyl (Dipy), and n is the number of diamagnetic ligands. Multifrequency NMR experiments allowed us to determine the effective paramagnetic shifts of the ligands (L = THF or Py) and the chemical equilibrium constant for [Eu(SQ)3(THF)2]. In addition, we have found a strong magnetic field effect on the NMR line broadening, giving rise to very broad NMR lines at high magnetic fields. We attribute this effect to broadening under fast exchange conditions when the NMR spectrum represents a homogeneously broadened line with a width proportional to the square of the NMR frequency difference of the free and bound forms of L. Consequently, the line width strongly increases with the magnetic field. This broadening effect allows one to determine relevant kinetic parameters, i.e., the effective exchange time. The strong broadening effect allows one to exploit the [Eu(SQ)3(THF)2] complex as an efficient shift reagent, which not only shifts unwanted NMR signals but also broadens them, notably, in high-field NMR experiments. We have also found that [Eu(SQ)3Dipy] is a thermodynamically stable complex; hence, one can study [Eu(SQ)3Dipy] solutions without special precautions. We report an X-ray structure of the [Eu(SQ)3Dipy]·C6D6 crystals that have been grown directly in an NMR tube. This shows that multifrequency NMR investigations of heterospin compound solutions not only provide thermodynamic and kinetic data for heterospin species but also can be useful for the rational design of stable heterospin complexes and optimization of synthetic approaches.

Crucial Role of Paramagnetic Ligands for Magnetostructural Anomalies in “Breathing Crystals”

Breathing crystals based on polymer-chain complexes of Cu(hfac)(2) with nitroxides exhibit thermally and light-induced magnetostructural anomalies in many aspects similar to a spin crossover. In the present work, we report the synthesis and investigation of a new family of Cu(hfac)(2) complexes with tert-butylpyrazolylnitroxides and their nonradical structural analogues. The complexes with paramagnetic ligands clearly exhibit structural rearrangements in the copper(II) coordination units and accompanying magnetic phenomena characteristic for breathing crystals. Contrary to that, their structural analogues with diamagnetic ligands do not undergo rearrangements in the copper(II) coordination environments. This confirms experimentally the crucial role of paramagnetic ligands and exchange interactions between them and copper(II) ions for the origin of magnetostructural anomalies in this family of molecular magnets.

Net spin and polarization components of the spin density for the single determinant in the basis of paired orbitals

AbstractA decomposition of the spin density into the net spin density and polarization density for the unrestricted Kohn–Sham (KS) determinant in the basis of Löwdin–Amos–Hall paired orbitals (PO) is derived. In PO basis set, the net spin part of spin density is only determined by the manifold of occupied α‐spin orbitals which do not overlap with occupied β‐spin orbitals. In its turn, the polarization part is associated with the pairs of overlapping α and β orbitals. The decreased overlap in these pairs corresponds to the increased degree of spin polarization. As an example of the developed spin density decomposition, the complex of FeO with nitrobenzene (taken in the state with spin projection of Sz = 2) is considered for the B3LYP solution revealing substantial spin contamination for the KS determinant. The spin density decomposition predicts for this complex appreciable polarization density over the whole complex while the net spin density remains counter intuitive almost intact at FeO center. This result changes presumed mechanism of metal‐to‐ligand transfer of unpaired electrons from paramagnetic center to diamagnetic ligand having a high electron affinity. © 2012 Wiley Periodicals, Inc.

Three‐Dimensional Porous Metal–Radical Frameworks Based on Triphenylmethyl Radicals

Lanthanide coordination polymers {[Ln(PTMTC)(EtOH)(2)H(2)O]·x H(2)O, y EtOH} [Ln=Tb (1), Gd (2), and Eu (3)] and {[Ln(αH-PTMTC)(EtOH)(2)H(2)O]·x H(2)O, y EtOH} [Ln=Tb (1'), Gd (2'), and Eu (3')] have been prepared by reacting Ln(III) ions with tricarboxylate-perchlorotriphenylmethyl/methane ligands that have a radical (PTMTC(3-)) or closed-shell (αH-PTMTC(3-)) character, respectively. X-ray diffraction analyses reveal 3D architectures that combine helical 1D channels and a fairly rare (6,3) connectivity described with the (4(2).8)·(4(4).6(2).8(5).10(4)) Schäfli symbol. Such 3D architectures make these polymers porous solids upon departure of the non-coordinated guest-solvent molecules as confirmed by the XRD structure of the guest-free [Tb(PTMTC)(EtOH)(2)H(2)O] and [Tb(αH-PTMTC)(EtOH)(2)H(2)O] materials. Accessible voids represent 40% of the cell volume. Metal-centered luminescence was observed in Tb(III) and Eu(III) coordination polymers 1' and 3', although the Ln(III)-ion luminescence was quenched when radical ligands were involved. The magnetic properties of all these compounds were investigated, and the nature of the {Ln-radical} (in 1 and 2) and the {radical-radical} exchange interactions (in 3) were assessed by comparing the behaviors for the radical-based coordination polymers 1-3 with those of the compounds with the diamagnetic ligand set. Whilst antiferromagnetic {radical-radical} interactions were found in 3, ferromagnetic {Ln-radical} interactions propagated in the 3D architectures of 1 and 2.

“Jumping Crystals”: Oxygen-Evolving Metal-Nitroxide Complexes

The crystals of heterospin complexes [M(hfac)(2)L(2)] (where M = Cu, Ni, Co, or Mn; hfac = hexafluoroacetylacetonate; and L = nitronyl nitroxide, 4,4,5,5-tetramethyl-2-(1-methyl-1H-imidazol-5-yl)-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl) were found to make unusual jumping motions. Under ambient conditions, the jumping and various displacements of crystals lasted for several weeks. The mechanical motion was accompanied by the cracking and disintegration of crystals, and a solid [M(hfac)(2)(L(1))(2)] complex with the corresponding imino nitroxide 4,4,5,5-tetramethyl-2-(1-methyl-1H-imidazol-5-yl)-4,5-dihydro-1H-imidazole-1-oxyl (L(1)) was detected. The jumping was accompanied by the spontaneous elimination of oxygen, the source of which was the nitronyl nitroxyl fragment of coordinated L. An X-ray study of [M(hfac)(2)L(2)] (where M = Cu, Ni, Co, or Mn) showed that the molecular structure of all [M(hfac)(2)L(2)] and their packing in the solid state were identical. The packing of [M(hfac)(2)L(2)] was concluded to be critical to the mechanical effect. In complexes with different stoichiometries or different sets of diamagnetic ligands ([Cu(hfac)(2)L](2), [Cu(hfac)(acac)L]·EtOH, [CuPiv(2)L(2)]·2CH(2)Cl(2), and [Cu(hfac)(2)L(2)Cu(2)Piv(4)]·3C(7)H(8) (where acac is acetylacetonate and Piv is trimethylacetate), or free L), the effect vanished when the packing changed.

Three‐Dimensional Open‐Frameworks Based on LnIIIIons and Open‐/Closed‐Shell PTM Ligands: Synthesis, Structure, Luminescence, and Magnetic Properties

A series of isostructural open-framework coordination polymers formulated as [Ln(dmf)(3)(ptmtc)] (Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5); PTMTC = polychlorotriphenylmethyl tricarboxylate) and [Ln(dmf)(2)H(2)O(αH-ptmtc)] (Ln = Sm (1'), Eu (2'), Gd (3'), Tb (4'), Dy (5')) have been obtained by treating Ln(III) ions with PTMTC ligands with a radical (PTMTC(3-)) or a closed-shell character (αH-PTMTC(3-)). X-ray diffraction analyses reveal that these coordination polymers possess 3D architectures that combine large channels and fairly rare lattice complex T connectivity. In addition, these compounds show selective framework dynamic sorption properties. For both classes of ligands, the ability to act as an antenna in Ln sensitization processes has been investigated. No luminescence was observed for compounds 1-5, and 3' because of the PTMTC(3-) ligand and/or Gd(III) ion characteristics. Conversely, photoluminescence measurements show that 1', 2', 4', and 5' emit dark orange, red, green, and dark cyan metal-centered luminescence. The magnetic properties of all of these compounds have been investigated. The nature of the {Ln-radical} exchange interaction in these compounds has been assessed by comparing the behavior of the radical-based coordination polymers 1-5 with those of the compounds with the diamagnetic ligand set. While antiferromagnetic {Sm-radical} interactions are found in 1, ferromagnetic {Ln-radical} interactions propagate in the 3D architectures of 3, 4, and 5 (Ln = Gd, Tb, and Dy, respectively). This procedure also provided access to information on the {Ln-Ln} exchange existing in these magnetic systems.

Enhanced Sensitivity and Resolution in 1H Solid-State NMR Spectroscopy of Paramagnetic Complexes under Very Fast Magic Angle Spinning

High-resolution NMR spectroscopy for paramagnetic complexes in solids has been rarely performed because of its limited sensitivity and resolution due to large paramagnetic shifts and associated technical difficulties. The present study demonstrates that magic angle spinning (MAS) at speeds exceeding 20 kHz provides unusually high sensitivity and excellent resolution in 1H solid-state NMR (SSNMR) for paramagnetic systems. Spinning-speed dependence of 1H MAS spectra showed that very fast MAS (VFMAS) at 24-28 kHz enhanced sensitivity by a factor of 12-18, compared with the sensitivity of 1H SSNMR spectra under moderate MAS at 10 kHz, for Cu(dl-alanine)2.H2O and Mn(acac)3, for which the spectral ranges due to 1H paramagnetic shifts reach 200 and 1000 ppm, respectively. It was theoretically and experimentally confirmed that the absolute sensitivity of 1H VFMAS for small paramagnetic complexes such as Cu(dl-alanine)2 can be an order of magnitude higher than that of equimolar diamagnetic ligands because of short 1H T1 ( approximately 1 ms) of the paramagnetic systems and improved sensitivity under VFMAS. On the basis of this demonstrated high sensitivity, 1H SSNMR micro analysis of paramagnetic systems in a nanomole scale is proposed. Applications were performed on two polymorphs of Cu(II)(8-quinolinol)2, which is a suppressor of human cancer cells. It was demonstrated that 1H VFMAS SSNMR spectra accumulated for 20 nmol of the polycrystalline samples in 10 min enabled one to distinguish alpha- and beta-forms of Cu(II)(8-quinolinol)2 on the basis of shift positions and line widths.

Magnetic behavior of a manganese(II) complex of nitroxide-substituted 1,3-di(4-pyridyl)benzene

Magnetic interaction between two magnetic metals separated by a sizable diamagnetic ligand is generally very weak. A new spin-introduced bidentate, N- t-butyl- N-oxy-3,5-dipyridylaniline ( 1) was designed and synthesized to explore the spin-introducing effect on sizable ligands. A Mn(hfac) 2 complex of 1 was prepared and its structure was elucidated by X-ray structure analysis. The complex 1·Mn(hfac) 2 has a one-dimensional helical alternate-chain structure; a double-helix structure is constructed by the two chains. The ferromagnetic interaction between Mn(II) and the nitroxide spins was observed. The analysis using Seiden's model allows the estimation of J = + 0.33 K for Mn(II)–nitroxide interaction. In accordance with this result, the N- t-butyl- N-oxy-3-pyridylaniline ( 2)-derived Mn(hfac) 2 complex, 2 2·Mn(hfac) 2, revealed a comparable magnetic interaction between the Mn(II) spin and the nitroxide spins, showing J = + 0.19 K by a trimer model analysis. Thus, the magnetic interaction between the Mn(II) ions can be improved by introduction of the nitroxide group into the diamagnetic bidentate through the spin communication between the nitroxide and Mn(II) spins.

Superexchange interaction between lanthanide ions. Spin-Hamiltonian calculations for the and superexchange

Exchange interaction between two lanthanide or actinide ions of configuration bridged by common diamagnetic ligands is theoretically studied using a modified version of the superexchange theory developed in this paper. Exchange spin Hamiltonians were calculated for the and dimers serving as models of the and - superexchange, respectively. Spin - orbit coupling and crystal field splitting of the configuration (resulting in the ground Kramers doublet and the effective spin of the metal ion), virtual transfers of electrons of the type - - via and valent orbitals of the bridging ligands, and exchange pathways in these dimers are considered in detail. The superexchange is found to be extremely anisotropic and very sensitive to the geometry of the dimer. The spin Hamiltonian of the dimer is , where the exchange parameters are rationalized in terms of and parameters referring, respectively, to the - and - pathways of the electron transfers, , and . The and values are analytically expressed through and overlap integrals, orbital energies and intra-ionic Slater parameters. Exchange interaction between ions in the dimer is described by an antiferromagnetic Ising Hamiltonian , where the z axis connects two metal ions. Unusual magnetic properties of (M = Li, Na, K and Rb) and oxides involving ions and distorted perovskite are discussed in the light of these theoretical results.

"Channel decomposition" of superexchange interactions in the valence-bond method.

A valence-bond (VB) study is made of the channel structure of indirect-exchange interactions between paramagnetic transition-metal cations via diamagnetic ligands. The Introduction briefly surveys the literature regarding the channel concept in molecular-orbital (MO), VB, and hybrid MO-VB treatments. A computationally convenient expression, well known in direct-exchange formalism, for the exchange-coupling constant J is extended with corrections due to biquadratic terms in the effective spin Hamiltonian. We present a decomposition of J into a sum of contributions from unpaired-electron pairs (channel sum). The validity of this decomposition is numerically confirmed.

Influence of anionic substitutions on hyperfine interactions and ionic ordering in ferrites

Since M~ssbauer spectrum parameters are quite sensitive to the nearest surroundings variation, the M~ssbauer spectroscopy enables one to obtain information concerning the cation and anion mutual distribution on the atomic level. The magnetic properties of dielectric crystals in relation to the types of the constituting cations and their distribution in nonequivalent sites is studied rather elaborately. But the problem of the anionic influence has been raised rather recently /1-3/. The magnetic ordering is explained by the magnetic ions exchange interaction through diamagnetic ligands. Thus the direct anionic influence on the exchange interactions and on magnetic microstructure formation should be expected. In order to investigate the anionic influence a M6ssbauer study of ferrites with various anionic substitution was carried out

Exchange interactions in tetranuclear copper(ii) complexes

Tetranuclear copper(II) complexes with a Cu 4O 4 core are one of the simplest cases of a three-dimensional arrangement of metal ions, bridged through diamagnetic ligands. As such, these complexes may be employed as models for three-dimensionally interacting systems. These complexes exhibit a broad geometrical variation related to their widely varying magnetic properties, the variation of the Cu 4O 4 core being interpreted as a type of plasticity. In some cases, dimeric or polymeric forms may be prepared in addition to the tetrameric variety under somewhat the same crystallization conditions. If exchange coupling contributes to catalytic processes, for example in solution, changes in the geometry of complexes must be taken into consideration in any discussion of the influence of interaction strengths on chemical reaction steps.

Indirect exchange interaction between two doubly bridged paramagnetic atoms. a coupled-cluster model study

A model analysis is made of the influence of the ligands and the geometrical structure on the exchange-coupling constant, ecc, between two paramagnetic cations doubly bridged by two diamagnetic ligands. The model is based on a four-center, six-electron description of the superexchange unit, symmetry D 2h, with 1s slater type orbitals. A coupled-cluster method is employed. First, SCF orbitals are constructed for the unpaired electrons neglecting the interactions between the cations. Then, using these nonorthogonal orbitals, the direct exchange is evaluated. In the latter step, the influence of the ligands is gradually diminished and the results are compared with those from complete configuration interaction. It is found that the Coulomb and exchange ligand potentials are important in the evaluation of the ecc. Further, the cation-ligand-cation angle for which the ecc is equal to zero is not sensitive to variations of the ligand-admixture coefficient in the cation orbitals. The values of the ecc, however, do change essentially. Finally, the usual application of the Heitler-London treatment is revised. It is shown that the off-diagonal Lagrange multipliers in the SCF procedures introduce non-negligible contributions of the ligands to the ecc.