Field-Induced Slow Magnetic Relaxation in an Octacoordinated Fe(II) Complex with Pseudo-D2d Symmetry: Magnetic, HF-EPR, and Theoretical Investigations.

An octacoordinated Fe(II) complex, [FeII(dpphen)2](BF4)2·1.3H2O (1; dpphen = 2,9-bis(pyrazol-1-yl)-1,10-phenanthroline), with a pseudo-D2d-symmetric metal center has been synthesized. Magnetic, high-frequency/-field electron paramagnetic resonance (HF-EPR), and theoretical investigations reveal that 1 is characterized by uniaxial magnetic anisotropy with a negative axial zero-field splitting (ZFS) (D ≈ -6.0 cm-1) and a very small rhombic ZFS (E ≈ 0.04 cm-1). Under applied dc magnetic fields, complex 1 exhibits slow magnetic relaxation at low temperature. Fitting the relaxation time with the Arrhenius mode combining Orbach and tunneling terms affords a good fit to all the data and yields an effective energy barrier (17.0 cm-1) close to the energy gap between the ground state and the first excited state. The origin of the strong uniaxial magnetic anisotropy for 1 has been clearly understood from theoretical calculations. Our study suggests that high-coordinated compounds featuring a D2d-symmetric metal center are promising candidates for mononuclear single-molecule magnets.

Anisotropic Change in the Magnetic Susceptibility of a Dynamic Single Crystal of a Cobalt(II) Complex.

Atypically anisotropic and large changes in magnetic susceptibility, along with a change in crystalline shape, were observed in a CoII complex at near room temperature. This was achieved by combining oxalate molecules, acting as rotor, and a CoII ion with unquenched orbital angular momentum. A thermally controlled 90° rotation of the oxalate counter anion triggered a symmetry-breaking ferroelastic phase transition, accompanied by contraction-expansion behavior (ca. 4.5 %) along the long axis of a rod-like single crystal. The molecular rotation induced a minute variation in the coordination geometry around the CoII ion, resulting in an abrupt decrease and a remarkable increase in magnetic susceptibility along the direction perpendicular and parallel to the long axis of the crystal, respectively. Theoretical calculations suggested that such an unusual anisotropic change in magnetic susceptibility was due to a substantial reorientation of magnetic anisotropy induced by slight disruption in the ideal D3 coordination environment of the complex cation.

A tetra-gonal polymorph of bis-[hydro-tris-(pyrazol-1-yl)borato]iron(II).

The title compound, [Fe(C(9)H(10)BN(6))(2)], is a polymorph of a compound reported previously [Oliver et al. (1980 ▶). Inorg. Chem.19, 165-168]. In the previous report, the compound crystallized in the monoclinic space group P2(1)/c (Z = 4), whereas the crystal symmetry of the compound reported here is tetra-gonal (P4(2)/ncm, Z = 4). The mol-ecular structure is comprised of two hydro-tris-(1-pyrazol-yl)borate ligands (Tp(-)) and a central Fe(II) ion, which is coordinated by six pyrazole N atoms from two two Tp(-) ligands, yielding a distorted bipyramidal FeN(6) geometry. The complete molecule exhibits symmetry 2/m.

Synthesis, crystal structures, and luminescent properties of phenoxo-bridged heterometallic trinuclear propeller- and sandwich-like Schiff-base complexes.

A series of phenoxo-bridged heterometallic Schiff-base trinuclear complexes Zn-M-Zn [M = Cd(II), Pb(II), Nd(III), Eu(III), Gd(III), Tb(III), and Dy(III)] have been synthesized by a rational structural design based on two symmetrical Schiff-base ligands N,N'-bis(3-methoxysalicylidene)propylene-1,3-diamine (H(2)L(a)) and N,N'-bis(3-methoxysalicylidene)benzene-1,2-diamine (H(2)L(b)). Single X-ray diffraction analysis reveals a similar molecular structure among the eight propeller-like and seven sandwich-type phenoxo-bridged Zn-M-Zn complexes. In the compounds Cd[Zn(L(a))Cl](2) (1), {Cd[Zn(L(b))Cl](2)}.H(2)O (2), {Pb[Zn(L(b))Cl](2)}.2H(2)O (4), {Nd[Zn(L(a))Cl](2)(H(2)O)}.0.5ZnCl(4) .2H(2)O (5), and{M(III)[Zn(L(a))Cl](2)(H(2)O)}.0.5ZnCl(4).2MeOH [M = Eu(7), Gd (9), Tb (11), and Dy (13)], two [Zn(L)Cl](-) units coordinate to the central metal ion as a tetradentate ligand using its four oxygen atoms, forming a two-blade propeller-like left-handed and right-handed chiral Zn-M-Zn configuration despite the racemic nature of the whole complexes. Compounds {Pb[Zn(L(a))Cl](2)}.MeOH (3), {Nd[Zn(L(b))Cl](2)(DMF)(OAc)}.CH(3)CN (6), {Eu[Zn(L(b))Cl](2)(DMF)(OAc)}.CH(3)CN (8), {Gd[Zn(L(b))Cl](2)(DMF)(2)}.Cl.2H(2)O (10), {Tb[Zn(L(b))Cl](2)(DMF)(2)}.Cl.2H(2)O (12), {Dy[Zn(L(b))Cl](2)(DMF)(2)}.Cl.2H(2)O (14), and {Pb[Zn(L(b))Cl](2)}.2H(2)O (15) exhibit a relatively rare sandwich-type structure with a central metal ion clamped by two [Zn(L)Cl](-) units. Photophysical studies indicate that all of the complexes exhibit luminescence both in solution and in solid sate, and there exists an energy transfer from the [Zn(L)Cl](-) unit to the central rare earth ions of Nd(III) (5 and 6), Tb(III) (11), and Dy(III) (for 13). In particular, systematic and comparative investigation of the photophysical properties of these trinuclear complexes reveals that the luminescence properties could easily be tuned by changing the central metal or the Schiff-base ligand.

Rational design and assembly of a new series of cyanide-bridged Fe(III)-Mn(II) one-dimensional single chain complexes: synthesis, crystal structures, and magnetic properties.

Two mononuclear seven-coordinated macrocycle manganese(II) compounds and three dicyanide-containing precursors have been employed as building blocks to assemble cyanide-bridged heterobimetallic complexes, resulting in five new cyanide-bridged single chain complexes {[Mn(L(1))][Fe(bpb)(CN)(2)]}ClO(4) x 0.5 H(2)O (2), {[Mn(L(2))][Fe(bpb)(CN)(2)]}ClO(4) x 0.5 H(2)O (3), {[Mn(L(1))][Fe(bpClb)(CN)(2)]}ClO(4) x H(2)O (4), {[Mn(L(2))][Fe(bpClb)(CN)(2)]}ClO(4) x 0.5 H(2)O (5), and {[Mn(L(1))][Fe(bpdBrb)(CN)(2)]}ClO(4) x H(2)O (6). Single X-ray diffraction analysis reveals their one-dimensional (1D) single cyanide-bridged cationic polymeric chain structure consisting of alternating units of [Mn(L)](2+) (L = L(1) or L(2)) and [Fe(L')(CN)(2)](-) (L' = bpb(2-), bpClb(2-) or bpdBrb(2-)) with free ClO(4)(-) as balanced anion. Similar to the mononuclear macrocyclic manganese(II) precursor {[Mn(L(2))(H(2)O)Cl]ClO(4)}.CH(3)OH (1), the coordination geometry of manganese(II) ion in all the 1D complexes is a slightly distorted pentagonal-bipyrimidal with two cyanide nitrogen atoms at the trans positions and N(5) or N(3)O(2) coordinating mode at the equatorial plane from ligand L(1) or L(2). Investigation of the magnetic properties of these five 1D single chain cyanide-bridged Fe(III)-Mn(II) complexes reveals the antiferromagnetic magnetic coupling between neighboring Fe(III) and Mn(II) ions through the bridging cyanide group. A best-fit to the magnetic susceptibilities of these complexes based on the 1D alternating chain model leads to the magnetic coupling constants J(1) = -1.16(2) and J(2) = -0.10(3) cm(-1) for 2, J(1) = -3.10(1) and J(2) = -0.25(1) cm(-1) for 3, J(1) = -1.10(1) and J(2) = -0.139(8) cm(-1) for 4, J(1) = -1.99(6) and J(2) = -0.57(1) cm(-1) for 5, and J(1) = -1.23(1) and J(2) = -0.13(5) cm(-1) for 6, respectively. This work will provide valuable information for the rational design and synthesis of low-dimensional, in particular, single chain, cyanide-bridged magnetic complexes.

Hydrogen-bond directed cyanide-bridged molecular magnets derived from polycyanidemetalates and Schiff base manganese(III) compounds: synthesis, structures, and magnetic properties.

A series of six new cyanide-bridged heterometallic complexes including two tetranuclear T-like Fe(III)Mn(III)(3) compounds, {[Mn(L(1))(H(2)O)](3)[Fe(CN)(5)(1-CH(3)im)]}ClO(4) x 1.5 H(2)O (1) and {[Mn(L(2))(H(2)O)](3)[Fe(CN)(5)(1-CH(3)im)]}ClO(4) x 3 H(2)O (2); two heptanuclear cage-shaped M(III)Mn(III)(6) (M = Fe, Cr) compounds, {[Mn(L(2))(H(2)O)](6)[Fe(CN)(6)]}[Fe(CN)(6)] x 6 CH(3)OH (3) and {[Mn(L(2))(H(2)O)](6)[Cr(CN)(6)]}[Cr(CN)(6)] x 6 CH(3)OH (4); and two two-dimensional M-Mn(III) networks, {[H(3)O][Mn(L(1))](2)[Fe(CN)(6)]} x 2 DMF (5) and {K[Mn(L(1))](2)[Cr(CN)(6)]} x 1.5 CH(3)CN x CH(3)OH (6) (L(1) = N,N-ethylene-bis(3-methoxysalicylideneiminate, L(2) = N,N-ethylene-bis(3-ethoxysalicylideneiminate) have been successfully assembled from three polycyanidemetalates containing five or six cyanide groups and two manganese(III) building blocks containing bicompartmental Schiff base ligands. The cyanide-bridged polynuclear complexes are self-complementary through a coordinated aqua ligand from one complex and the free O(4) compartment from the neighboring complex, giving supramolecular one-dimensional ladders and three-dimensional networks for 1 and 2 and for 3 and 4, respectively. Investigation over magnetic susceptibilities of the six complexes reveals the overall ferromagnetic interactions for complexes 1, 2, 3, and 5 and antiferromagnetic interaction for 4 and 6. Compounds 1-4 show some characteristics of metamagnet behavior at low temperatures due to the relatively strong intermolecular hydrogen-bonding interaction. The two complexes with two-dimensional structure exhibit three-dimensional antiferromagnetic ordering with typical metamagnetic behavior below 8.4 K for 5 and 11.5 K for 6, respectively. The present result appears to add new members to the very few examples of polynuclear clusters exhibiting 3D magnetic ordering relying on intermolecular interactions, to the best of our knowledge, which will be helpful for providing valuable information for the understanding and application of intermolecular hydrogen-bonding interactions in the molecular magnetic materials.

Bis(diethyl-enetriamine-κN,N',N'')nickel(II) bis-(1,2-dicyanoethene-1,2-dithiolato-κS,S')nickel(II).

The title compound, [Ni(C(4)H(13)N(3))(2)][Ni(C(4)N(2)S(2))(2)], has been synthesized by the reaction of Ni(ClO(4))(2)·6H(2)O, diethyl-enetriamine (deta) and Na(2)[Ni(mnt)(2)] [mnt = maleonitrile-dithiol-ate(2-)] in methanol. The structure is composed of a [Ni(deta)(2)](2+) cation and a [Ni(mnt)(2)](2-) anion. The coordination geometry of the Ni(II) ion in the cation is slightly distorted octa-hedral, defined by six N atoms from two deta ligands, while the Ni(II) ion in the anion is four-coordinated by four S atoms from two mnt ligands in a slightly distorted square-planar geometry. The cations and anions are connected by N-H⋯N hydrogen bonds.

A series of 4,5,9,10-tetrahydropyrene-based tetraarylethenes: synthesis, structures and solid-state emission behavior.

By controlling the number of 4,5,9,10-tetrahydropyrene segments around the tetraarylethene core, a series of 4,5,9,10-tetrahydropyrene-based tetraarylethenes were synthesized and structurally characterized. An aggregation-induced emission (AIE) study indicated that all the compounds are AIE active: they are weak emitters in good solvents but highly emissive in the condensed phase, and hence are potential solid-state emitters. Their optical properties, electrochemical properties and theoretical calculations were investigated, and the results prove that the π-conjugation degree of these compounds increases with the increasing number of 4,5,9,10-tetrahydropyrene units. However, the fluorescence quantum yield in the solid state doesn't increase with increasing π-conjugation. We studied the reason for this by analyzing the crystal structures of some compounds, and proposed that the close degree of molecular packing in the solid state may be responsible for it. Loose packing of tetraarylethenes in the solid state can restrict the rotation of the aromatic rings but cannot constrain other non-radiative pathways efficiently, such as vibration, which leads to the unpredictable emission of the compounds.

Water-controlled synthesis and single-crystal structural transformations of a cyanide-bridged W(IV)-Ni(II) molecular wheel complex and 3D networks.

One cyanide-bridged W(IV)-Ni(II) wheel-like complex and two three-dimensional (3D) networks can be directly synthesized based on K4[W(CN)8] and [Ni(L)](ClO4)2 precursors by controlling the quantity of water in organic solvent. The water-controlled single-crystal structural transformations among these complexes are described.

Heterobimetallic porphyrin-based single-chain magnet constructed from manganese(III)-porphyrin and trans-dicyanobis(acetylacetonato) ruthenate(III) containing co-crystallized bulk anions and cations.

Two cyanide-bridged alternated 1 : 1 Ru(III)/Mn(III) complexes structurally characterized as single-chain containing co-crystallized bulk anions and cations have been successfully assembled from [Mn(TPP)(H(2)O)(2)](+) and [Ru(acac)(2)(CN)(2)](-) blocks. Systematic investigation of their magnetic properties reveals typical single-chain magnet (SCM) behaviors for both of them.

Supramolecular metallomacrocycles based on trans-dicyanoferrite(III) building blocks: synthesis, crystal structure and magnetic properties.

The reaction of trans-[Fe(R-bpb)(CN)2]- (R-bpb2-=R-substituted-1,2-bis(pyridine-2-carboxamido)benzenate) with trans-Mn(III) Schiff base complexes [Mn(5-X-saltn)]ClO4 (5-X-saltn2-=N,N'-propanolbis(5-X-substituted-salcylideneiminato) dianion) gave rise to cyanide-bridged neutral binuclear [MnFe] compounds [Mn(saltn)(MeOH)][Fe(bpb)(CN)2].3H2O (), [Mn(saltn)(H2O)Fe(bpmb)(CN)2].H2O (), [Mn(saltn)(MeOH)Fe(bpClb)(CN)2].2H2O (), and ionic [Mn2Fe]+-[Fe]- complexes [Mn2(5-Br-saltn)2(H2O)(EtOH)Fe(bpb)(CN)2][Fe(bpb)(CN)2].6H2O () and [Mn2(5-Cl-saltn)2(CH3OH)(EtOH)Fe(bpb)(CN)2][Fe(bpb)(CN)2].5H2O.MeCN (). Four binuclear units of complexes assemble in a head-to-tail way via hydrogen bonding giving rise to a metallo-supramolecular [MnFe]4 square, while two [Mn2Fe]+-[Fe]- units of complexes form a metallo-supramolecular macrocyclic structure. Magnetic studies reveal that complexes and exhibit intermetallic ferromagnetic coupling, while complex displays antiferromagnetic interaction between low-spin Fe(III) and high-spin Mn(III) through the cyanide bridges. Complexes , and display frequency dependent of current-alternating (ac) magnetic susceptibility, typical of the presence of slow magnetization relaxation. Because of the existence of intermolecular magnetic interaction, complex shows an exchange-biased single-molecule magnet (SMM) behavior below 0.5 K.

Synthesis, structure, and magnetic properties of cyanide-bridged low-dimensional heterometallic Fe(III)-Mn(II) complexes.

With trans-dicyanideiron(III) precursor K[Fe(salen)(CN)(2)] x CH(3)OH (1) (H(2)salen = N,N'-bis(salicyl)ethylenediamine) as a building block, four new cyanide-bridged heterometallic Fe(III)-Mn(II) complexes {[Fe(salen)(CN)(2)](2)[Mn(bipy)(2)]} x CH(3)OH x 2 H(2)O (2), {[Fe(salen)(CN)(2)](2)[Mn(phen)(2)]} x CH(3)OH (3), and {[Fe(salen)(CN)(2)][Mn(L)]}ClO(4) x CH(3)OH [L = L(a) (4) and L(b) (5)] have been successfully assembled. Single X-ray diffraction analyses reveals the trinuclear Fe(III)(2)Mn(II) nature of complexes 2 and 3 comprised of one [Mn(bipy)(2)](2+)/[Mn(phen)(2)](2+) and two [Fe(salen)(CN)(2)](-) units, and the one-dimensional cyanide-bridged cationic polymeric single chain nature of complexes 4 and 5 consisting of alternating units of [Mn(L)](2+) (L = L(a) and L(b)) and [Fe(salen)(CN)(2)](-) with free ClO(4)(-) as balanced anions. Investigations into the magnetic properties of these four heterometallic cyanide-bridged Fe(III)-Mn(II) complexes reveals the overall antiferromagnetic interaction between neighbouring Fe(III) and Mn(II) ions through the bridging cyanide group. On the basis of the Hamiltonian H = -2JS(Mn)(S(Fe(1)) + S(Fe(2))), the magnetic simulation for the trimeric complexes 2 and 3 gives the magnetic coupling constant 2J(MnFe) = -2.68(4) cm(-1) for 2 and 2J(MnFe) = -2.46(8) cm(-1) for 3, respectively. A best-fit to the magnetic susceptibilities of 4 and 5 based on the one-dimensional alternating chain model leads to the magnetic coupling constants 2J(1) = -6.50(2) and 2J(2) = -1.57(1) cm(-1) for 4 and 2J(1) = -5.35(2) and 2J(2) = -0.93(1) cm(-1) for 5.

Cyanide-bridged Mn(III)-Fe(III) bimetallic complexes based on the pentacyano(1-methylimidazole)ferrate(III) building block: structure and magnetic characterizations.

Seven cyanide-bridged bimetallic complexes have been synthesized by the reaction of [Fe(1-CH3im)(CN)5]2- with Mn(III) Schiff base complexes. Their crystal structure and magnetic properties have been characterized. Five complexes, [Mn2(5-Brsalen)2Fe(CN)5(1-CH3im)] x H2O (1), [Mn2(5-Clsalen)2(H2O)2Fe(CN)5(1-CH3im)] x H2O (2), [Mn2(5-Clsaltn)2(H2O)2Fe(CN)5(1-CH3im)] (3), [Mn2(5-Clsaltmen)2(H2O)2Fe(CN)5(1-CH3im)] x H2O (4), and [Mn2(5-Brsaltmen)2(H2O)2Fe(CN)5(1-CH3im)] x CH3OH (5), are neutral and trinuclear with two [Mn(SB)]+ (SB2- = Schiff base ligands) and one [Fe(1-CH3im)(CN)5]2-. Complex {[Et4N][Mn(acacen)Fe(CN)5(1-CH3im)]}n x 6nH2O (6) is one-dimensional with alternate [Mn(acacen)]+ and [Fe(CN)5(1-CH3im)]2- units. The two-dimensional complex {[Mn4(saltmen)4Fe(CN)5(1-CH3im)]}n[ClO4]2n x 9nH2O (7) consists of Mn4Fe units which are further connected by the phenoxo oxygen atoms. Magnetic studies show the presence of ferromagnetic Mn(III)-Fe(III) coupling in the trinuclear compounds with the magnetic coupling constant (J) ranging from 4.5 to 6.0 cm-1, based on the Hamiltonian H = -2JSFe(SMn(1) + SMn(2)). Antiferromagnetic interaction has been observed in complex 6, whereas ferromagnetic coupling occurs in complex 7. Complexes 6 and 7 exhibit long-range magnetic ordering with a TN value of 4.0 K for 6 and Tc of 4.8 K for 7. Complex 6 shows metamagnetic behavior at 2 K, and complex 7 possesses a hysteresis loop with a coercive field of 500 Oe, typical of a soft ferromagnet.

Substituent effect on formation of heterometallic molecular wheels: synthesis, crystal structure, and magnetic properties.

The reaction of manganese(III) Schiff bases of the type salen(2-) (N,N'-ethylenebis(salicylideneaminato)) with X-substituted (X = CH(3), Cl) pyridinecarboxamide dicyanoferrite(III) [Fe(X-bpb)(CN)(2)](-) gave rise to a series of cyanide-bridged Mn(6)Fe(6) molecular wheels, [Mn(III)(salen)](6)[Fe(III)(bpmb)(CN)(2)](6) x 7H(2)O (1), [Mn(salen)](6)[Fe(bpClb)(CN)(2)](6) x 4H(2)O x 2CH(3)OH (2), [Mn(salen)](6)[Fe(bpdmb)(CN)(2)](6) x 10H(2)O x 5CH(3)OH (3), [Mn(5-Br(salpn))](6)[Fe(bpmb)(CN)(2)](6) x 24H(2)O x 8CH(3)CN (4), and [Mn(5-Cl(salpn))](6)[Fe(bpmb)(CN)(2)](6) x 25H(2)O x 5CH(3)CN (5). Compared with [Fe(bpb)(CN)(2)](-), which always gives rise to 1D or polynuclear species when reacting with Mn(III) Schiff bases, the introduction of substituents (X) to the bpb(2-) ligand has a driving force in formation of the novel wheel structure. Magnetic studies reveal that high-spin ground state S = 15 is present in the wheel compounds originated from the ferromagnetic Mn(III)-Fe(III) coupling. For the first time, the quantum Monte Carlo study has been used to modulate the magnetic susceptibility of the huge Mn(6)Fe(6) metallomacrocycles, showing that the magnetic coupling constants J range from 3.0 to 8.0 K on the basis of the spin Hamiltonian [Formula: see text]. Hysteresis loops for 1 have been observed below 0.8 K, indicative of a single-molecule magnet with a blocking temperature (TB) of 0.8 K. Molecular wheels 2-5 exhibit frequency dependence of alternating-current magnetic susceptibility under zero direct-current magnetic field, signifying the slow magnetization relaxation similar to that of 1. Significantly, an unprecedented archlike Mn(2)Fe(2) cluster, [Mn(5-Cl(salpn))](2)[Fe(bpmb)(CN)(2)](2) x 3H(2)O x CH(3)CN (6), has been isolated as an intermediate of the Mn(6)Fe(6) wheel 5. Ferromagnetic Mn(III)-Fe(III) coupling results in a high-spin S = 5 ground state. Combination of the high-spin state and a negative magnetic anisotropy (D) results in the observation of slow magnetization relaxation in 6.

Mu1,1-azide-bridged ferromagnetic MnIII dimer with slow relaxation of magnetization.

A new end-on azide-bridged dimeric Mn(III) complex has been synthesized by using the tridentate N-isonicotinamidosalicylaidimine ligand. Magnetic studies show that the complex has a high-spin ground state of S = 4 and is ac out-of-phase frequency-dependent.

A novel one-dimensional complex: catena-poly[[manganese(III)-di-mu-2-[(2-hydroxyethyl)iminomethyl]phenolato-kappa2O1,N:kappaO2;kappaO2:kappa2O1] chloride].

In the title one-dimensional complex, [[Mn(III)(C9H10NO2)2]Cl]n, the Schiff base ligand 2-[(2-hydroxyethyl)iminomethyl]phenolate (Hsae-) functions as both a bridging and a chelating ligand. The Mn(III) ion is six-coordinated by two N and four O atoms from four different Hsae- ligands, yielding a distorted MnO4N2 octahedral environment. Each [Mn(III)(Hsae)2]+ cationic unit has the Mn atom on an inversion centre and each [Mn(III)(Hsae)2]+ cation lies about another inversion centre. The chain-like complex is further extended into a three-dimensional network structure through Cl...H-O hydrogen bonds and C-H...pi contacts involving the Hsae- rings.

[Fe(bpb)(CN)2]- as a versatile building block for the design of novel low-dimensional heterobimetallic systems: synthesis, crystal structures, and magnetic properties of cyano-bridged Fe(III)-Ni(II) complexes [(bpb)(2-) = 1,2-bis(pyridine-2-carboxamido)benzenate].

A dicyano-containing [Fe(bpb)(CN)2]- building block has been employed for the synthesis of cyano-bridged heterometallic Ni(II)-Fe(III) complexes. The presence of steric bpb(2-) ligand around the iron ion results in the formation of low-dimensional species: five are neutral NiFe2 trimers and three are one-dimensional (1D). The structure of the 1D complexes consists of alternating [NiL]2+ and [Fe(bpb)(CN)2]- generating a cyano-bridged cationic polymeric chain and the perchlorate as the counteranion. In all complexes, the coordination geometry of the nickel ions is approximately octahedral with the cyano nitrogen atoms at the trans positions. Magnetic studies of seven complexes show the presence of ferromagnetic interaction between the metal ions through the cyano bridges. Variable temperature magnetic susceptibility investigations of the trimeric complexes yield the following J(NiFe) values (based on the spin exchange Hamiltonian H = -2J(NiFe) S(Ni) (S(Fe(1)) + S(Fe(2))): J(NiFe) = 6.40(5), 7.8(1), 8.9(2), and 6.03(4) cm(-1), respectively. The study of the magneto-structural correlation reveals that the cyanide-bridging bond angle is related to the strength of magnetic exchange coupling: the larger the Ni-N[triple bond]C bond angle, the stronger the Ni- - -Fe magnetic interaction. One 1D complex exhibits long-range antiferromagnetic ordering with T(N) = 3.5 K. Below T(N) (1.82 K), a metamagnetic behavior was observed with the critical field of approximately 6 kOe. The present research shows that the [Fe(bpb)(CN)2]- building block is a good candidate for the construction of low-dimensional magnetic materials.

mer-[Fe(pcq)(CN)3]-: a novel cyanide-containing building block and its application to assembling cyanide-bridged trinuclear FeIII2MnII complexes [pcq- = 8-(pyridine-2-carboxamido)quinoline anion].

A new cyanide-containing building block K[Fe(pcq)(CN)(3)] [1; pcq(-) = 8-(pyridine-2-carboxamido)quinoline anion] containing a low-spin Fe(III) center with three cyanide groups in a meridional arrangement has been successfully designed and synthesized. Three cyanide-bridged trinuclear Fe(III)(2)Mn(II) complexes, [Fe(pcq)(CN)(3)](2)[Mn(CH(3)OH)(2)(H(2)O)(2)].2H(2)O (2), [Fe(pcq)(CN)(3)](2)[Mn(bipy)(2)].CH(3)OH.2H(2)O (3), and [Fe(pcq)(CN)(3)](2)[Mn(phen)(2)].CH(3)OH.2H(2)O (4), have been synthesized and structurally characterized. The magnetic susceptibilities of the three heterometallic complexes have been investigated.

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.