Mixed-metal sandwich complexes [M(II)2(H2O)2Fe(III)2(P2W15O56)2]14- (M(II) = Co, Mn): synthesis and stability. The molecular structure of [M(II)2(H2O)2Fe(III)2(P2W15O56)2]14-

Two new mixed-metal sandwich complexes [M(II)2(H2O)2Fe(III)2(P2W15O56)2]14- (abbreviated [M2Fe2P4W30], M(II) = Co(II), Mn(II)) were obtained at pH 3 by addition of M2+ to [Na2(H2O)2Fe(III)2(P2W15O56)2]16- (abbreviated [Na2Fe2P4W30]) without substitution in the alpha-[P2W15O56]12- (abbreviated [P2W15]) units. Their X-ray structures are reported. At lower pH, back conversion to [Na2Fe2P4W30] was followed by 31P NMR, electrochemistry and UV-visible spectroscopy. The preparation and the characterization in solution of the lacunary intermediate [NaCo(II)(H2O)2Fe(III)2(P2W15O56)2]15- (abbreviated [NaCoFe2P4W30]) is also described.     

Increasing the ordering temperatures in oxalate-based 3D chiral magnets: the series [Ir(ppy)2(bpy)][M(II)M(III)(ox)3] x 0.5 H2O (M(II)M(III) = MnCr, FeCr, CoCr, NiCr, ZnCr, MnFe, FeFe); bpy = 2,2'-bipyridine; ppy = 2-phenylpyridine; ox = oxalate dianion)

The synthesis, structure, and physical properties of a novel series of oxalate-based bimetallic magnets obtained by using the Ir(ppy)2(bpy)]+ cation as a template of the bimetallic [M(II)M(III)(ox)3]- network are reported. The compounds can be formulated as [Ir(ppy)2(bpy)][M(II)Cr(III)(ox)3] x 0.5 H2O (M(II) = Ni, Mn, Co, Fe, and Zn) and [Ir(ppy)2(bpy)]-[M(II)Fe(III)(ox)3] x 0.5 H2O (M(II) = Fe, Mn) and crystallize in the chiral cubic space group P4(1)32 or P4(3)32. They show the well-known 3D chiral structure formed by M(II) and M(III) ions connected through oxalate anions with [Ir(ppy)2(bpy)]+ cations and water molecules in the holes left by the oxalate network. The M(II)Cr(III) compounds behave as soft ferromagnets with ordering temperatures up to 13 K, while the Mn(II)Fe(III) and Fe(II)Fe(III) compounds behave as a weak ferromagnet and a ferrimagnet, respectively, with ordering temperatures of 31 and 28 K. These values represent the highest ordering temperatures so far reported in the family of 3D chiral magnets based on bimetallic oxalate complexes.     

Cyano-bridged Mn(III)3M(III) (M(III) = Fe, Cr) complexes: synthesis, structure, and magnetic properties

Two cyano-bridged tetranuclear complexes composed of Mn(III) salen (salen = N,N'-ethylene bis(salicylideneiminate)) and hexacyanometalate(III) (M = Fe, Cr) in a stoichiometry of 3:1 have been selectively synthesized using {NH2(n-C12H25)2}3[M(III)(CN)6] (M(III) = Fe, Cr) starting materials: [{Mn(salen)(EtOH)}3{M(CN)6}] (M = Fe, 1; Cr, 2). Compounds 1 and 2 are isostructural with a T-shaped structure, in which [M(CN)6]3- assumes a meridional-tridentate building block to bind three [Mn(salen)(EtOH)]+ units. The strong frequency dependence and observation of hysteresis on the field dependence of the magnetization indicate that 1 is a single-molecule magnet.     

Self-assembled decanuclear Na(I)2Mn(II)4Mn(III)4 complexes: from discrete clusters to 1-D and 2-D structures, with the Mn(II)4Mn(III)4 unit displaying a large spin ground state and probable SMM behaviour

The synthesis, magnetic characterization and X-ray crystal structures are reported for five new manganese compounds, [Mn(III)(teaH(2))(sal)]·(1/2)H(2)O (1), [Na(I)(2)Mn(II)(4)Mn(III)(4)(teaH)(6)(sal)(4)(N(3))(2)(MeOH)(4)]·6MeOH (2), [Na(I)(2)Mn(II)(4)Mn(III)(4)(teaH)(6)(sal)(4)(N(3))(2)(MeOH)(2)](n)·7MeOH (3), [Na(I)(2)Mn(II)(4)Mn(III)(4)(teaH)(6)(sal)(4)(N(3))(2)(MeOH)(2)](n)·2MeOH·Et(2)O (4) and [K(I)(2)Mn(II)(4)Mn(III)(4)(teaH)(6)(sal)(4)(N(3))(2)(H(2)O)(2)](n)·5MeOH (5). Complex 1 is a mononuclear compound, formed via the reaction of Mn(NO(3))(2)·4H(2)O, triethanolamine (teaH(3)) and salicylic acid (salH(2)) in a basic methanolic solution. Compound 2 is a mixed-valent hetero-metallic cluster made up of a Mn(8)Na(2) decanuclear core and is formed via the reaction of sodium azide (NaN(3)) with 1. Compounds 3-5 are isolated as 1- or 2-D coordination polymers, each containing the decanuclear Mn(8)M(2) (M = Na(+) or K(+)) core building block as the repeating unit. Compound 3 is isolated when 1 is reacted with NaN(3) over a very short reaction time and forms a 1-D coordination polymer. Each unit displays inter-cluster bridges via the O-atoms of teaH(2-) ligands bonding to the sodium ions of an adjacent cluster. Increasing the reaction time appears to drive the formation of 4 which forms 2-D polymeric sheets and is a packing polymorph of 3. The addition of KMnO(4) and NaN(3) to 1 resulted in compound 5, which also forms a 1-D coordination polymer of the decanuclear core unit. The 1-D chains are now linked via inter-cluster potassium and salicylate bridges. Solid state DC susceptibility measurements were performed on compounds 1-5. The data for 1 are as expected for an S = 2 Mn(III) ion, with the isothermal M vs. H data being fitted by matrix diagonalization methods to give values of g and the axial (D) and rhombic (E) zero field splitting parameters of 2.02, -2.70 cm(-1) and 0.36 cm(-1) respectively. The data for 2-5, each with an identical Mn(II)(4)Mn(III)(4) metallic core, indicates large spin ground states, with likely values of S = 16 (±1) for each. Solid state AC susceptibility measurements confirm the large spin ground state values and is also suggestive of SMM behaviour for 2-5 as observed via the onset of frequency dependent out-of-phase peaks.     

New valence-sandwich [Mn(II)4Mn(III)4Mn(II)4] aggregate showing single-molecule magnet behavior

The reaction of manganese(II) acetate, 1,1,1-tris(hydroxymethyl)methane (H3thme), and triethylamine in methanol leads to the formation of [Mn12O2(OMe)2(thme)4(OAc)10(H2O)4].2MeOH. The [Mn(III)4Mn(II)8] core consists of a central [Mn(III)4O6] rhombus sandwiched by two [Mn(II)4O7] fragments. Frequency-dependent ac susceptibility and hysteresis loops in the magnetization indicate single-molecule magnet behavior with a pure quantum-tunneling regime of relaxation below 0.2 K.     

Cyano-bridged Mn(III)-M(III) single-chain magnets with M(III)=Co(III), Fe(III), Mn(III), and Cr(III)

A series of isostructural cyano-bridged Mn(III)(h.s.)-M(III)(l.s.) alternating chains, [Mn(III)(5-TMAMsalen)M(III)(CN)(6)]?4H(2)O (5-TMAMsalen(2-)=N,N'-ethylenebis(5-trimethylammoniomethylsalicylideneiminate), Mn(III)(h.s.)=high-spin Mn(III), M(III)(l.s.)=low-spin Co(III), Mn-Co; Fe(III), Mn-Fe; Mn(III), Mn-Mn; Cr(III), Mn-Cr) was synthesized by assembling [Mn(III)(5-TMAMsalen)](3+) and [M(III)(CN)(6)](3-). The chains present in the four compounds, which crystallize in the monoclinic space group C2/c, are composed of an [-Mn(III)-NC-M(III)-CN-] repeating motif, for which the -NC-M(III)-CN- motif is provided by the [M(III)(CN)(6)](3-) moiety adopting a trans bridging mode between [Mn(III)(5-TMAMsalen)](3+) cations. The Mn(III) and M(III) ions occupy special crystallographic positions: a C(2) axis and an inversion center, respectively, forming a highly symmetrical chain with only one kind of cyano bridge. The Jahn-Teller axis of the Mn(III)(h.s.) ion is perpendicular to the N(2)O(2) plane formed by the 5-TMAMsalen tetradentate ligand. These Jahn-Teller axes are all perfectly aligned along the unique chain direction without a bending angle, although the chains are corrugated with an Mn-N(axis) -C angle of about 144°. In the crystal structures, the chains are well separated with the nearest inter-chain M???M distance being relatively large at 9?? due to steric hindrance of the bulky trimethylammoniomethyl groups of the 5-TMAMsalen ligand. The magnetic properties of these compounds have been thoroughly studied. Mn-Fe and Mn-Mn display intra-chain ferromagnetic interactions, whereas Mn-Cr is characterized by an antiferromagnetic exchange that induces a ferrimagnetic spin arrangement along the chain. Detailed analyses of both static and dynamic magnetic properties have demonstrated without ambiguity the single-chain magnet (SCM) behavior of these three systems, whereas Mn-Co is merely paramagnetic with S(Mn)=2 and D/k(B)=-5.3?K (D being a zero-field splitting parameter). At low temperatures, the Mn-M compounds with M=Fe, Mn, and Cr display remarkably large M versus H hysteresis loops for applied magnetic fields along the easy magnetic direction that corresponds to the chain direction. The temperature dependence of the associated relaxation time for this series of compounds systematically exhibits a crossover between two Arrhenius laws corresponding to infinite-chain and finite-chain regimes for the SCM behavior. These isostructural hetero-spin SCMs offer a unique series of alternating [-Mn-NC-M-CN-] chains, enabling physicists to test theoretical SCM models between the Ising and Heisenberg limits.     

Single-molecule magnet behavior in heterometallic M(II)-Mn(III)(2)-M(II) tetramers (M(II) = Cu, Ni) containing Mn(III) salen-type dinuclear core

The linear-type heterometallic tetramers, [Mn(III)(2)(5-MeOsaltmen)(2)M(II)(2)(L)(2)](CF(3)SO(3))(2) x 2H(2)O (MII = Cu, 1a; Ni, 2a), where 5-MeOsaltmen(2-) = N,N'-(1,1,2,2-tetramethylethylene) bis(5-methoxysalicylideneiminate), and H(2)L = 3-{2-[(2-hydroxy-benzylidene)-amino]-2-methyl-propylimino}-butan-2-one oxime, have been synthesized and characterized from structural and magnetic points of view. These two compounds are isostructural and crystallize in the same monoclinic P2(1)/n space group. The structure has a [M(II)-NO-Mn(III)-(O)(2)-Mn(III)-ON-M(II)] skeleton, where -NO- is a linking oximato group derived from the non-symmetrical Schiff-base complex [M(II)(L)] and -(O)(2)- is a biphenolato bridge in the out-of-plane [Mn(2)(5-MeOsaltmen)(2)](2+) dimer. The solvent-free compounds, 1b and 2b, have also been prepared by drying of the parent compounds, 1a and 2a, respectively, at 100 degrees C under dried nitrogen. After this treatment, the crystallinity is preserved, and 1b and 2b crystallize in a monoclinic P2(1)/c space group without significant changes in their structures in comparison to 1a and 2a. Magnetic measurements on 1a and 1b revealed antiferromagnetic Mn(III)---Cu(II) interactions via the oximato group and weak ferromagnetic Mn(III)---Mn(III) interactions via the biphenolato bridge leading to an S(T) = 3 ground state. On the other hand, the diamagnetic nature of the square planar Ni(II) center generates an S(T) = 4 ground state for 2a and 2b. At low temperature, these solvated (a) and desolvated (b) compounds display single-molecule magnet behavior modulated by their spin ground state.     

Oxalate-based soluble 2D magnets: the series [K(18-crown-6)]3[M(II)3(H2O)4{M(III)(ox)3}3] (M(III) = Cr, Fe; M(II) = Mn, Fe, Ni, Co, Cu; ox = C2O4(2-); 18-crown-6 = C12H24O6)

The synthesis and magnetic properties of the oxalate-based molecular soluble magnets with general formula [K(18-crown-6)] 3[M (II) 3(H 2O) 4{M (III)(ox) 3} 3] (M (III) = Cr, Fe; M (II) = Mn, Fe, Ni, Co, Cu; ox = C 2O 4 (2-)) are here described. All the reported compounds are isostructural and built up by 2D bimetallic networks formed by alternating M (III) and M (II) ions connected through oxalate anions. Whereas the Cr (III)M (II) derivatives behave as ferromagnets with critical temperatures up to 8 K, the Fe (III)M (II) present ferri- or weak ferromagnetic ordering up to 26 K.     

Single-molecule magnets constructed from cyanometalates: {[Tp*Fe(III)(CN)3M(II)(DMF)4]2[OTf]2} x 2DMF (M(II) = Co, Ni)

Treatment of several divalent transition-metal trifluoromethanesulfonates [M(II)(OTf)2; M(II) = Mn, Co, Ni] with [NEt4][Tp*Fe(III)(CN)3] [Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate] in DMF affords three isostructural rectangular clusters of {[Tp*Fe(III)(CN)3M(II)(DMF)4]2[OTf]2} x 2DMF (M(II) = Mn, 3; Co, 4; Ni, 5) stoichiometry. Magnetic studies of 3-5 indicate that the Tp*Fe(CN)3(-) centers are highly anisotropic and exhibit antiferromagnetic (3 and 4) and ferromagnetic (5) exchange to afford S = 4, 2, and 3 spin ground states, respectively. ac susceptibility measurements suggest that 4 and 5 exhibit incipient single-molecule magnetic behavior below 2 K.     

Tetranuclear polybipyridyl complexes of Ru(II) and Mn(II), their electro- and photo-induced transformation into di-mu-oxo Mn(III)Mn(IV) hexanuclear complexes

Three heterotetranuclear complexes, [{Ru(II)(bpy)(2)(L(n))}(3)Mn(II)](8+) (bpy = 2,2'-bipyridine, n = 2, 4, 6), in which a Mn(II)-tris-bipyridine-like centre is covalently linked to three Ru(II)-tris-bipyridine-like moieties using bridging bis-bipyridine L(n) ligands, have been synthesised and characterised. The electrochemical, photophysical and photochemical properties of these complexes have been investigated in CH(3)CN. The cyclic voltammograms of the three complexes exhibit two successive very close one-electron metal-centred oxidation processes in the positive potential region. The first, which is irreversible, corresponds to the Mn(II)/Mn(III) redox system (E(pa) approximately 0.82 V vs Ag/Ag(+) 0.01 M in CH(3)CN-0.1 M Bu(4)NClO(4)), whereas the second which is, reversible, is associated with the Ru(II)/Ru(III) redox couple (E(1/2) approximately 0.91 V). In the negative potential region, three successive reversible four electron systems are observed, corresponding to ligand-based reduction processes. The three stable dimeric oxidized forms of the complexes, [Mn(2)(III,IV)O(2){Ru(II)(bpy)(2)(L(n))}(4)](11+), [Mn(2)(IV,IV)O(2){Ru(II)(bpy)(2)(L(n))}(4)](12+) and [Mn(2)(IV,IV)O(2){Ru(III)(bpy)(2)(L(n))}(4)](16+) are obtained in fairly good yields by sequential electrolyses after consumption of respectively 1.5, 0.5 and 3 electrons per molecule of initial tetranuclear complexes. The formation of the di-micro-oxo binuclear complexes are the result of the instability of the {[Ru(II)(bpy)(2)(L(n))](3)Mn(III)}(9+) species, which react with residual water, via a disproportionation reaction and the release of one ligand, [Ru(II)(bpy)(2)(L(n))](2+). A quantitative yield can be obtained for these reactions if the electrochemical oxidations are performed in the presence of an added external base like 2,6-dimethylpyridine. Photophysical properties of these compounds have been investigated showing that the luminescence of the Ru(II)-tris-bipyridine-like moieties is little affected by the presence of manganese within the tetranuclear complexes. A slight quenching of the excited states of the ruthenium moieties, which occurs by an intramolecular process, has been observed. Measurements made at low concentration (<1 x 10(-5) M) indicate that some decoordination of Mn(2+) arises in 1a-c. These measurements allow the calculation of the association constants for these complexes. Finally, photoinduced oxidation of the tetranuclear complexes has been performed by continuous photolysis experiments in the presence of a large excess of a diazonium salt, acting as a sacrificial oxidant. The three successive oxidation processes, Mn(II)--> Mn(III)Mn(IV), Mn(III)Mn(IV)--> Mn(IV)Mn(IV) and Ru(II)--> Ru(III) are thus obtained, the addition of 2,6-dimethylpyridine in the medium giving an essentially quantitative yield for the two first photo-induced oxidation steps as found for electrochemical oxidation.     

Assembly of azido- or cyano-bridged binuclear complexes containing the bulky [Mn(phen)2]2+ building block: syntheses, crystal structures, and magnetic properties

Two new cyano-bridged heterobinuclear complexes, [Mn(II)(phen)2Cl][Fe(III)(bpb)(CN)2] x 0.5CH3CH2OH x 1.5H2O (1) and [Mn(II)(phen)2Cl][Cr(III)(bpb)(CN)2] x 2H2O (2) [phen = 1,10-phenanthroline; bpb(2-) = 1,2-bis(pyridine-2-carboxamido)benzenate], and four novel azido-bridged Mn(II) dimeric complexes, [Mn2(phen)4(mu(1,1)-N3)2][M(III)(bpb)(CN)2]2 x H2O [M = Fe (3), Cr (4), Co (5)] and [Mn2(phen)4(mu(1,3)-N3)(N3)2]BPh4 x 0.5H2O (6), have been synthesized and characterized by single-crystal X-ray diffraction analysis and magnetic studies. Complexes 1 and 2 comprise [Mn(phen)2Cl]+ and [M(bpb)(CN)2]- units connected by one cyano ligand of [M(bpb)(CN)2]-. Complexes 3-5 are doubly end-on (EO) azido-bridged Mn(II) binuclear complexes with two [M(bpb)(CN)2]- molecules acting as charge-compensating anions. However, the Mn(II) ions in complex 6 are linked by a single end-to-end (EE) azido bridging ligand with one large free BPh4(-) group as the charge-balancing anion. The magnetic coupling between Mn(II) and Fe(III) or Cr(III) in complexes 1 and 2 was found to be antiferromagnetic with J(MnFe) = -2.68(3) cm(-1) and J(MnCr) = -4.55(1) cm(-1) on the basis of the Hamiltonian H = -JS(Mn)S(M) (M = Fe or Cr). The magnetic interactions between two Mn(II) ions in 3-5 are ferromagnetic in nature with the magnetic coupling constants of 1.15(3), 1.05(2), and 1.27(2) cm(-1) (H = -JS(Mn1)S(Mn2)), respectively. The single EE azido-bridged dimeric complex 6 manifests antiferromagnetic interaction with J = -2.29(4) cm(-1) (H = -JS(Mn1)S(Mn2)). Magneto-structural correlationship on the EO azido-bridged Mn(II) dimers has been investigated.     

Density functional study on geometrical features and electronic structures of di-mu-oxo-bridged [Mn2O2(H2O)8]q+ with Mn(II), Mn(III), and Mn(IV)

We report the geometrical features and electronic structures of di-mu-oxo-bridged Mn-Mn binuclear complexes with H2O ligands [Mn2O2(H2O)8]q+ in the iso- and mixed-valence oxidation states. All of the combinations among Mn(II), Mn(III), and Mn(IV) ions are considered the oxidation states of the Mn-Mn center, and the changes in molecular structure induced by the different electron configurations of Mn-based orbitals are investigated in relation to the oxygen-evolving complex (OEC) of photosystem II. The stable geometries of complexes are determined by using the hybrid-type density functional theory for both of the highest- and lowest-spin couplings between Mn sites, and the lowest-spin-coupled states are energetically more favorable than the highest-spin-coupled states except in the case of the complexes with the Mn(II) ion. The coordination positions of H2O ligands at the Mn(II) site tend to shift from the octahedral positions in contrast to those at the Mn(III) and Mn(IV) sites. The shape of the Mn2O2 core and the distances between the Mn ions and the H2O ligands vary depending on the electron occupations of the octahedral eg orbitals on the Mn site with an antibonding nature for the Mn-ligand interactions, indicating the trend as Mn(II)-O > Mn(III)-O and Mn(IV)-O, O-Mn(II)-O > O-Mn(III)-O > O-Mn(IV)-O among the iso-valence Mn2O2 cores, and O-Mn(lower)-O < O-Mn(higher)-O within the mixed-valence Mn2O2 core, and as Mn(II)-OH2 and Mn(III)-OH2 > Mn(IV)-OH2 for the axial H2O ligand. The optimized geometries of model complexes are compared with the X-ray structure of the OEC, and it is suggested that the cubane-like Mn cluster of the active site may not contain a Mn(II) ion. The effective exchange integrals are estimated by applying the approximate spin projection to clarify the magnetic coupling between Mn sites, and the superexchange pathways through the di-mu-oxo bridge are examined on the basis of the singly occupied magnetic orbitals derived from the singlet-coupled natural orbitals in the broken-symmetry state. The comparisons of the calculated results between [Mn2O2(H2O)8]q+ in this study and [Mn2O2(NH3)8]q+ reported by McGrady et al. suggest that the symmetric pathways are dominant to the exchange coupling constant, and the crossed pathway would be less important for the former than it would for the latter in the Mn(III)-Mn(III), Mn(IV)-Mn(IV), and Mn(III)-Mn(IV) oxidation states.     

New mixed-valent Mn clusters from the use of N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (edteH4): Mn3, Mn4, Mn6, and Mn10

The syntheses, crystal structures, and magnetochemical characterization are reported for the new mixed-valent Mn clusters [Mn(2)(II)Mn(III)(O(2)CMe)(2)(edteH(2))(2)](ClO(4)) (1), [Mn(II)(2)Mn(III)(2)(edteH(2))(2)(hmp)(2)Cl(2)](Mn(II)Cl(4)) (2), [Mn(III)(6)O(2)(O(2)CBu(t))(6)(edteH)(2)(N(3))(2)] (3), [Na(2)Mn(III)(8)Mn(II)(2)O(4)(OMe)(2)(O(2)CEt)(6)(edte)(2)(N(3))(6)] (4), and (NEt(4))(2)[Mn(8)(III)Mn(2)(II)O(4)(OH)(2)-(O(2)CEt)(6)(edte)(2)(N(3))(6)](5), where edteH(4) is N,N,N',N'-tetrakis-(2-hydroxyethyl)ethylenediamine and hmpH is 2-(hydroxymethyl)pyridine. 1-5 resulted from a systematic exploration of the effect of different Mn sources, carboxylates, the presence of azide, and other conditions, on the Mn/edteH(4) reaction system. The core of 1 consists of a linear Mn(II)Mn(III)Mn(II) unit, whereas that of 2 is a planar Mn(4) rhombus within a [Mn(II)(2)Mn(III)(2)(μ(3)-OR)(2)] incomplete-dicubane unit. The core of 3 comprises a central [Mn(III)(4)(OR)(2)] incomplete-dicubane on either side of which is edge-fused a triangular [Mn(III)(3)(μ(3)-O)] unit. The cores of 4 and 5 are similar and consist of a central [Mn(II)(2)Mn(III)(2)(μ(3)-OR)(2)] incomplete-dicubane on either side of which is edge-fused a distorted [Mn(II)Mn(III)(3)(μ(3)-O)(2)(μ(3)-OR)(2)] cubane unit. Variable-temperature, solid-state direct current (dc) and alternating current (ac) magnetization studies were carried out on 1-5 in the 5.0-300 K range, and they established the complexes to have ground state spin values of S = 3 for 1, S = 9 for 2, and S = 4 for 3. The study of 3 provided an interesting caveat of potential pitfalls from particularly low-lying excited states. For 4 and 5, the ground state is in the S = 0-4 range, but its identification is precluded by a high density of low-lying excited states.     

Molecular and electronic structures of bis(pyridine-2,6-diimine)metal complexes [ML2](PF6)n (n = 0, 1, 2, 3; M = Mn, Fe, Co, Ni, Cu, Zn)

A series of mononuclear, octahedral first-row transition metal ion complexes mer-[M(II)L0(2)](PF6)2 containing the tridentate neutral ligand 2,6-bis[1-(4-methoxyphenylimino)ethyl]pyridine (L0) and a Mn(II), Fe(II), Co(II), Ni(II), Cu(II), or Zn(II) ion have been synthesized and characterized by X-ray crystallography. Cyclic voltammetry and controlled potential coulometry show that each dication (except those of Cu(II) and Zn(II)) can be reversibly one-electron-oxidized, yielding the respective trications [M(III)L0(2)]3+, and in addition, they can be reversibly reduced to the corresponding monocations [ML2]+ and the neutral species [ML2]0 by two successive one-electron processes. [MnL2]PF6 and [CoL2]PF6 have been isolated and characterized by X-ray crystallography; their electronic structures are described as [Mn(III)L1(2)]PF6 and [Co(I)L0(2)]PF6 where (L1)1- represents the one-electron-reduced radical form of L0. The electronic structures of the tri-, di-, and monocations and of the neutral species have been elucidated in detail by a combination of spectroscopies: UV-vis, NMR, X-band EPR, Mossbauer, temperature-dependent magnetochemistry. It is shown that pyridine-2,6-diimine ligands are noninnocent ligands that can be coordinated to transition metal ions as neutral L0 or, alternatively, as monoanionic radical (L1)1-. All trications are of the type [M(III)L0(2)]3+, and the dications are [M(II)L0(2)]2+. The monocations are described as [Mn(III)L1(2)]+ (S = 0), [Fe(II)L0L1]+ (S = 1/2), [Co(I)L0(2)]+ (S = 1), [Ni(I)L0(2)]+ (S = 1/2), [Cu(I)L0(2)]+ (S = 0), [Zn(II)L1L0]+ (S = 1/2) where the Mn(II) and Fe(II) ions are low-spin-configurated. The neutral species are described as [Mn(II)L1(2)]0, [Fe(II)L1(2)]0, [Co(I)L0L1]0, [Ni(I)L0L1]0, and [Zn(II)L1(2)]0; their electronic ground states have not been determined.     

Novel biscapped and monocapped tris(dioxime) Mn(II) complexes: x-ray crystal structure of the first cationic tris(dioxime) Mn(II) complex [Mn(CDOH)3BPh]OH (CDOH2= 1,2-cyclohexanedione dioxime)

This report describes the synthesis and characterization of a series of novel biscapped and monocapped tris(dioxime) Mn(II) complexes [Mn(dioxime)3(BR)2] and [Mn(dioxime)3BR]+ (dioxime = cyclohexanedione dioxime (CDOH2) and 1,2-dimethylglyoxyl dioxime (DMGH(2)); R = Me, n-Bu, and Ph). All tris(dioxime) Mn(II) complexes have been characterized by elemental analysis, IR, UV/vis, cyclic voltammetry, ESI-MS, and, in the cases of [Mn(CDOH)3BPh]OH.CHCl3 and [Mn(CDO)(CDOH)2(BBu(OC2H5))2], X-ray crystallography. It was found that biscapped Mn(II) complexes [Mn(dioxime)3(BR)2] are not stable in the presence of water and readily hydrolyze to form monocapped cationic complexes [M(dioxime)3BR]+. This instability is most likely caused by mismatch between the size of Mn(II) and the coordination cavity of the biscapped tris(dioxime) ligands. In contrast, monocapped cationic complexes [M(dioxime)3BR]+ are very stable in aqueous solution even in the presence of PDTA (1,2-diaminopropane-N,N,N',N'-tetraacetic acid) because of the kinetic inertness imposed by the monocapped tris(dioxime) chelators that are able to completely "wrap" Mn(II) into their N6 coordination cavity. [Mn(CDO)3BPh]OH has a distorted trigonal prismatic coordination geometry, with the Mn(II) being bonded by six imine-N donors. The hydroxyl groups from three dioxime chelating arms form very strong intramolecular hydrogen bonds with the hydroxide counterion so that the structure of [Mn(CDOH)3BPh]OH can be considered as being the clathrochelate with the hydroxide counterion as a "cap".     

Highly anisotropic orbitally dependent superexchange in cyano-bridged clusters containing Mn(III) and Mn(II) ions.

We study the orbitally dependent magnetic exchange in cyanide-based clusters as a source of the barrier for reversal magnetization. We consider the Mn(III)-CN-Mn(II) dimer and linear Mn(II)-NC-Mn(III)-CN-Mn(II) trimer containing octahedrally coordinated Mn(III) and Mn(II) ions with special emphasis on the magnetic manifestations of the orbital degeneracy of the Mn(III) ion. The kinetic exchange mechanism involves the electron transfer from the single occupied t(2) orbitals of the Mn(II) ion [6A1(t2(3)e2) ground state] to the singly occupied t(2) orbitals of the Mn(III) ion [3T1(t2(4)) ground state] resulting in the charge-transfer 5T2(t2(2)e2)Mn(III) - 2T2(t2(5))Mn(II) state of the pair. The deduced effective exchange Hamiltonian that takes into account orbital degeneracy leads to an essentially non-Heisenberg energy pattern. The energy levels are shown to be dependent on both spin and orbital quantum numbers, thus providing direct information about the magnetic anisotropy of the system. Along with the magnetic exchange, the model includes an axial component of the crystal field and spin-orbit coupling operating within the ground 3T1(t2(4)) cubic term of the Mn(III) ion. We have shown that under certain conditions both named interactions lead to the occurrence of the barrier for the reversal of magnetization, which significantly increases when passing from the dimer to the trimer. This provides a possible way for raising the magnetic barrier in the family of cyano-bridged manganese clusters.     

Complexation of [S,S,S]- and [R,S,R]-isomers of N-bis [2-(1,2-dicarboxyethoxy)ethyl] aspartic acid with Mg(II), Ca(II), Mn(II), Fe(III), Cu(II) and Zn(II) ions in aqueous solution

In a search for environmentally friendly metal chelating ligands for industrial applications, the protonation and complex formation equilibria of [S,S,S]- and [R,S,R]-isomers of N-bis[2-(1,2-dicarboxyethoxy)ethyl] aspartic acid (BCA6) with Mg(II), Ca(II), Mn(II), Fe(III), Cu(II) and Zn(II) ions in aqueous 0.1 M NaCl solution were studied at 25°C by potentiometric titration. The model for complexation and the stability constants of the different complexes were determined for each metal ion using the computer program SUPERQUAD. With all metal ions (M ⁿ⁺), stable ML ^n?6 complexes dominated complex formation for both isomers. Differences in complexation models were found for binuclear species.     

Octanuclearity and tetradecanuclearity in manganese chemistry: an octanuclear manganese(II)/(III) complex featuring the novel [Mn8(mu4-O)2(mu3-OH)2]14+ core and [Mn10(II)Mn4(III)O4(O2CMe)20[(2-py)2C(OH)O]4] (2-py = 2-pyridyl)

Reactions of Mn sources with di-2-pyridyl ketone, (2-py)2CO, and phenyl 2-pyridyl ketone oxime, (ph)(2-py)CNOH, give the novel clusters [Mn10(II)Mn4(III)O4(O2CMe)20[(2-py)2C(OH)O]4] 1 and [Mn4(II)Mn4(III)O2(OH)2(O2CPh)10[(ph)(2-py)CNO]4] 2, respectively, which possess low-spin ground states; the observed tetradecanuclearity in 1 is extremely rare in 3d-metal chemistry, while the core of 2 has a unique topology consisting of two linked [Mn2(II)Mn2(III)O(OH)] units.     

Calix[4]arene supported clusters: a dimer of [Mn(III)Mn(II)] dimers

Phosphinate ligands allow for the transformation of a calix[4]arene supported [Mn(III)(2)Mn(II)(2)] tetramer cluster motif into an unusual [Mn(III)Mn(II)](2) dimer of dimers; the clusters self-assemble in the crystal to form bi-layer arrays reminiscent of the typical packing of calixarene solvates.     

Spectroscopic, thermal and biological studies of the coordination compounds of sulfasalazine drug: Mn(II), Hg(II), Cr(III), ZrO(II), VO(II) and Y(III) transition metal complexes

The complexations of sulfasalazine (H3Suz) with some of transition metals have been investigated. Three types of complexes, [Mn(HSuz)-2(H2O)4] x 2H2O, [M(HSuz)-2(H2O)2] x xH2O (M=Hg(II), ZrO(II) and VO(II), x=4, 8 and 6, respectively) and [M(HSuz)-2(Cl)(H2O)3] x xH2O (M=Cr(III) and Y(III), x=5 and 6, respectively) were obtained and characterized by physicochemical and spectroscopic methods. The IR spectra of the complexes suggest that the H3Suz behaves as a bidentate ligand. The thermal decomposition of the complexes as well as thermodynamic parameters (DeltaE*, DeltaH*, DeltaS* and DeltaG*) were estimated using Coats-Redfern and Horowitz-Metzger equations. In vitro antimicrobial activities of the H3Suz and the complexes were tested.