Field-Induced Single-Ion Magnet Behavior in Nickel(II) Complexes with Functionalized 2,2':6'-2″-Terpyridine Derivatives: Preparation and Magneto-Structural Study.

Two mononuclear nickel(II) complexes of the formula [Ni(terpyCOOH)2](ClO4)2∙4H2O (1) and [Ni(terpyepy)2](ClO4)2 MeOH (2) [terpyCOOH = 4'-carboxyl-2,2':6',2″-terpyridine and terpyepy = 4'-[(2-pyridin-4-yl)ethynyl]-2,2':6',2″-terpyridine] have been prepared and their structures determined by single-crystal X-ray diffraction. Complexes 1 and 2 are mononuclear compounds, where the nickel(II) ions are six-coordinate by the six nitrogen atoms from two tridentate terpy moieties. The mean values of the equatorial Ni-N bond distances [2.11(1) and 2.12(1) Å for Ni(1) at 1 and 2, respectively, are somewhat longer than the axial ones [2.008(6) and 2.003(6) Å (1)/2.000(1) and 1.999(1) Å (2)]. The values of the shortest intermolecular nickel-nickel separation are 9.422(1) (1) and 8.901(1) Å (2). Variable-temperature (1.9-200 K) direct current (dc) magnetic susceptibility measurements on polycrystalline samples of 1 and 2 reveal a Curie law behavior in the high-temperature range, which corresponds to magnetically isolated spin triplets, the downturn of the χMT product at lower temperatures being due to zero-field splitting effects (D). Values of D equal to -6.0 (1) and -4.7 cm-1 (2) were obtained through the joint analysis of the magnetic susceptibility data and the field dependence of the magnetization. These results from magnetometry were supported by theoretical calculations. Alternating current (ac) magnetic susceptibility measurements of 1 and 2 in the temperature range 2.0-5.5 K show the occurrence of incipient out-phase signals under applied dc fields, a phenomenon that is characteristic of field-induced Single-Molecule Magnet (SMM) behavior, which herein concerns the 2 mononuclear nickel(II) complexes. This slow relaxation of the magnetization in 1 and 2 has its origin in the axial compression of the octahedral surrounding at their nickel(II) ions that leads to negative values of D. A combination of an Orbach and a direct mechanism accounts for the field-dependent relation phenomena in 1 and 2.

Trinuclear Cobalt(II) Triple Helicate with a Multidentate Bithiazolebis(oxamate) Ligand as a Supramolecular Nanomagnet.

The cobalt(II)-mediated self-assembly of the potentially tris(chelating) N,N'-2,2'-(4,4'-bithiazole)bis(oxamate) (dabtzox) ligand gives a new metal-organic supramolecular nanomagnet of formula K6Co3(dabtzox)3·8H2O·MeOH (1) featuring a unique linear triple-stranded trinuclear structure of the helicate type.

Holmium(III) Single-Ion Magnet for Cryomagnetic Refrigeration Based on an MRI Contrast Agent Derivative.

The coexistence of field-induced blockage of the magnetization and significant magnetocaloric effects in the low-temperature region occurs in a mononuclear holmium(III) diethylenetriamine-N,N,N',N″,N″-pentaacetate complex, whose gadolinium(III) analogue is a commercial MRI contrast agent. Both properties make it a suitable candidate for cryogenic magnetic refrigeration, thus enlarging the variety of applications of this simple class of multifunctional molecular nanomagnets.

Incorporation of CrIII into a Keggin Polyoxometalate as a Chemical Strategy to Stabilize a Labile {CrIIIO4} Tetrahedral Conformation and Promote Unattended Single-Ion Magnet Properties.

Polyoxometalates (POMs) provide rigid and highly symmetric coordination sites and can be used as a strategy for the stabilization of magnetic ions. Herein, we report a new member of the Keggin archetype, the Cr-centered Keggin anion [α-CrW12O40]5- (CrW12), with the unusual tetrahedral coordination of CrIII reported for the first time in POMs conferring unattended magnetic properties. POM chemistry has recently presented excellent examples of single-molecule and single-ion magnets (SMMs and SIMs) as well as molecular spin qubits; however, the majority of POM-based SIMs reported to date contain lanthanoid ions. CrW12, as the first example of a chromium(III) SIM, exhibits slow relaxation of magnetization and quantum tunneling with a single-ion magnetic behavior even above 10 K with an energy barrier for the reversal of the magnetization of 3.0 K. The first 3d-metal SIM based on a nonlacunary Keggin anion is the foundation for a new research area in POM chemistry.

Single-Ion Magnetic Behaviour in an Iron(III) Porphyrin Complex: A Dichotomy Between High Spin and 5/2-3/2 Spin Admixture.

A mononuclear iron(III) porphyrin compound exhibiting unexpectedly slow magnetic relaxation, which is a characteristic of single-ion magnet behaviour, is reported. This behaviour originates from the close proximity (≈550 cm-1 ) of the intermediate-spin S=3/2 excited states to the high-spin S=5/2 ground state. More quantitatively, although the ground state is mostly S=5/2, a spin-admixture model evidences a sizable contribution (≈15 %) of S=3/2 to the ground state, which as a consequence experiences large and positive axial anisotropy (D=+19.2 cm-1 ). Frequency-domain EPR spectroscopy allowed the mS = |±1/2⟩→|±3/2⟩ transitions to be directly accessed, and thus the very large zero-field splitting in this 3d5 system to be unambiguously measured. Other experimental results including magnetisation, Mössbauer, and field-domain EPR studies are consistent with this model, which is also supported by theoretical calculations.

Single-Molecule-Magnet FeII4FeIII2 and Antiferromagnetic FeIII4 Coordination Clusters.

Supported by endogenous (part of the ligand, in-built) phenoxo bridges provided by the ligand 2,6-bis[{{(5-bromo-2-hydroxybenzyl)}{(2-(pyridylethyl)}amino}methyl]-4-methylphenol) (H3L), in its deprotonated form, exogenous (not part of the ligand, externally added or generated) oxo-/hydroxo- and acetato-bridged [FeII4FeIII2(O)2(O2CMe)4(L)2]·4Et2O (1) and [FeIII4(OH)2(O2CMe)3(L)2](ClO4)·3MeCN·2H2O (2) coordination clusters have been synthesized and structurally characterized. Complexes 1 and 2 have µ4-O and µ3-OH bridges, respectively. Magnetic studies on 1 reveal slow magnetic relaxation below 2 K. Both in-phase ( χ'M) and out-of-phase (χ″M) magnetic susceptibility were found to be frequency dependent. This is typical of a single-molecule magnet (SMM) with τ0 = 1.9(2) × 10-7 s-1 and Ea = 5.1(3) cm-1. Assuming that Ea corresponds to the energy splitting of the ground spin state ( S = 2) by the zero-filed-splitting (zfs), Ea = 4| D| ( D is the axial zfs parameter), D ≈ - 1.3 cm-1 could be estimated. For 2, three types of magnetic interactions are observed: JA = -56.5(3), JB = -71.6(4), and JC = +4.5(2) cm-1. Considering the observed structural parameters, the magnetic behavior for both of the coordination clusters 1 and 2 has been rationalized.

Magnetic Molecular Conductors Based on Bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) and the Tris(chlorocyananilato)ferrate(III) Complex.

Electrocrystallization of the bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) organic donor in the presence of the [Fe(ClCNAn)3]3- tris(chlorocyananilato)ferrate(III) paramagnetic anion in different stoichiometric ratios and solvent mixtures afforded two different hybrid systems formulated as [BEDT-TTF]4[Fe(ClCNAn)3]·3H2O (1) and [BEDT-TTF]5[Fe(ClCNAn)3]2·2CH3CN (2) (An = anilato). Compounds 1 and 2 present unusual structures without the typical segregated organic and inorganic layers, where layers of 1 are formed by Λ and Δ enantiomers of the anionic paramagnetic complex together with mixed-valence BEDT-TTF tetramers, while layers of 2 are formed by Λ and Δ enantiomers of the paramagnetic complex together with dicationic BEDT-TTF dimers and monomers. Compounds 1 and 2 show semiconducting behaviors with room-temperature conductivities of ca. 6 × 10-3 S cm-1 (ambient pressure) and 1 × 10-3 S cm-1 (under applied pressure of 12.1 GPa), respectively, due to strong dimerization between the donors. Magnetic measurements performed on compound 1 indicate weak antiferromagnetic coupling between high-spin FeIII (SFe = 5/2) and mixed-valence radical cation diyads (BEDT-TTF)2+ (Srad = 1/2) mediated by the anilate ligands, together with an important Pauli paramagnetism typical for conducting systems.

Coligand Effects on the Field-Induced Double Slow Magnetic Relaxation in Six-Coordinate Cobalt(II) Single-Ion Magnets (SIMs) with Positive Magnetic Anisotropy.

Two mononuclear cobalt(II) compounds of formula [Co(dmphen)2(OOCPh)]ClO4·1/2H2O·1/2CH3OH (1) and [Co(dmbipy)2(OOCPh)]ClO4 (2) (dmphen = 2,9-dimethyl-1,10-phenanthroline, dmbipy = 6,6'-dimethyl-2,2'-bipyridine and HOOCPh = benzoic acid) are prepared and magnetostructurally investigated. Each cobalt(II) ion is six-coordinate with a distorted octahedral CoN4O2 environment. The complex cations are interlinked leading to supramolecular chains (1) and pairs (2) that grow along the crystallographic c-axis with racemic mixtures of (Δ,Λ)-Co units. FIRMS allowed us to directly measure the zero-field splitting between the two lowest Kramers doublets, which led to axial anisotropy values of 58.3 cm-1 ≤ D < 60.7 cm-1 (1) and 63.8 cm-1 ≤ D < 64.1 cm-1 (2). HFEPR spectra of polycrystalline samples of 1 and 2 at low temperatures confirm the positive sign of D and provide an estimate of the E/D quotient [0.147/0.187 (1) and 0.052 (2)]. Detailed ac and dc magnetic studies reveal that 1 and 2 are new examples of field-induced single-ion magnets (SIMs) with small transversal anisotropy. CASSCF/NEVPT2 calculations support these results. Two Orbach processes or one Orbach plus a direct relaxation mechanism provide similar agreements with the nonlinear experimental Arrhenius plots at Hdc = 500 and 2500 G for 1. Two independent relaxation processes occur in 2, but in contrast to 1, an observed linear dependence of ln(τ) vs 1/T substantiates Orbach processes against the most widely proposed Raman and direct mechanisms. The analysis of each relaxation process in 2 provided values for Ea and τ0 that are very close to those found for 1, validating the predominant role of the Orbach relaxations in both compounds and, probably, also in other cobalt(II) SIMs. A mechanism based on a spin-phonon coupling is proposed to account for the SIM behavior in 1 and 2 with any Raman or direct processes being discarded.

Cytosine Nucleobase Ligand: A Suitable Choice for Modulating Magnetic Anisotropy in Tetrahedrally Coordinated Mononuclear CoII Compounds.

A family of tetrahedral mononuclear CoII complexes with the cytosine nucleobase ligand is used as the playground for an in-depth study of the effects that the nature of the ligand, as well as their noninnocent distortions on the Co(II) environment, may have on the slow magnetic relaxation effects. Hence, those compounds with greater distortion from the ideal tetrahedral geometry showed a larger-magnitude axial magnetic anisotropy (D) together with a high rhombicity factor (E/D), and thus, slow magnetic relaxation effects also appear. In turn, the more symmetric compound possesses a much smaller value of the D parameter and, consequently, lacks single-ion magnet behavior.

Photoluminescent and Slow Magnetic Relaxation Studies on Lanthanide(III)-2,5-pyrazinedicarboxylate Frameworks.

In the series described in this work, the hydrothermal synthesis led to oxidation of the 5-methyl-pyrazinecarboxylate anion to the 2,5-pyrazinedicarboxylate dianion (2,5-pzdc) allowing the preparation of three-dimensional (3D) lanthanide(III) organic frameworks of formula {[Ln2(2,5-pzdc)3(H2O)4]·6H2O}n [Ln = Ce (1), Pr (2), Nd (3), and Eu (4)] and {[Er2(2,5-pzdc)3(H2O)4]·5H2O}n (5). Single-crystal X-ray diffraction on 1-5 reveals that they crystallize in the triclinic system, P1̅ space group with the series 1-4 being isostructural. The crystal structure of the five compounds are 3D with the lanthanide(III) ions linked through 2,5-pzdc2- dianions acting as two- and fourfold connectors, building a binodal 4,4-connected (4·648)(426282)-mog network. The photophysical properties of the Nd(III) (3) and Eu(III) (4) complexes exhibit sensitized photoluminescence in the near-infrared and visible regions, respectively. The photoluminescence intensity and lifetime of 4 were very sensitive due to the luminescence quenching of the 5D0 level by O-H oscillators of four water molecules in the first coordination sphere leading to a quantum efficiency of 11%. Variable-temperature magnetic susceptibility measurements for 1-5 reveal behaviors as expected for the ground terms of the magnetically isolated rare-earth ions [2F5/2, 2H4, 4I9/2, 7F0, and 4I15/2 for Ce(III), Pr(III), Nd(III), Eu(III), and Er(III), respectively] with MJ = 0 (2 and 4) and ±1/2 (1, 3, and 5). Q-band electron paramagnetic resonance measurements at low temperature corroborate these facts. Frequency-dependent alternating-current magnetic susceptibility signals under external direct-current fields in the range of 100-2500 G were observed for the Kramers ions of 1, 3, and 5, indicating slow magnetic relaxation (single-ion magnet) behavior. In these compounds, τ-1 decreases with decreasing temperature at any magnetic field, but no Arrhenius law can simulate such a dependence in all the temperature range. This dependence can be reproduced by the contributions of direct and Raman processes, the Raman exponent (n) reaching the expected value (n = 9) for a Kramers system.

Dicopper(II) metallacyclophanes as multifunctional magnetic devices: a joint experimental and computational study.

Metallosupramolecular complexes constitute an important advance in the emerging fields of molecular spintronics and quantum computation and a useful platform in the development of active components of spintronic circuits and quantum computers for applications in information processing and storage. The external control of chemical reactivity (electro- and photochemical) and physical properties (electronic and magnetic) in metallosupramolecular complexes is a current challenge in supramolecular coordination chemistry, which lies at the interface of several other supramolecular disciplines, including electro-, photo-, and magnetochemistry. The specific control of current flow or spin delocalization through a molecular assembly in response to one or many input signals leads to the concept of developing a molecule-based spintronics that can be viewed as a potential alternative to the classical molecule-based electronics. A great variety of factors can influence over these electronically or magnetically coupled, metallosupramolecular complexes in a reversible manner, electronic or photonic external stimuli being the most promising ones. The response ability of the metal centers and/or the organic bridging ligands to the application of an electric field or light irradiation, together with the geometrical features that allow the precise positioning in space of substituent groups, make these metal-organic systems particularly suitable to build highly integrated molecular spintronic circuits. In this Account, we describe the chemistry and physics of dinuclear copper(II) metallacyclophanes with oxamato-containing dinucleating ligands featuring redox- and photoactive aromatic spacers. Our recent works on dicopper(II) metallacyclophanes and earlier ones on related organic cyclophanes are now compared in a critical manner. Special focus is placed on the ligand design as well as in the combination of experimental and computational methods to demonstrate the multifunctionality nature of these metallosupramolecular complexes. This new class of oxamato-based dicopper(II) metallacyclophanes affords an excellent synthetic and theoretical set of models for both chemical and physical fundamental studies on redox- and photo-triggered, long-distance electron exchange phenomena, which are two major topics in molecular magnetism and molecular electronics. Apart from their use as ground tests for the fundamental research on the relative importance of the spin delocalization and spin polarization mechanisms of the electron exchange interaction through extended π-conjugated aromatic ligands in polymetallic complexes, oxamato-based dicopper(II) metallacyclophanes possessing spin-containing electro- and chromophores at the metal and/or the ligand counterparts emerge as potentially active (magnetic and electronic) molecular components to build a metal-based spintronic circuit. They are thus unique examples of multifunctional magnetic complexes to get single-molecule spintronic devices by controlling and allowing the spin communication, when serving as molecular magnetic couplers and wires, or by exhibiting bistable spin behavior, when acting as molecular magnetic rectifiers and switches. Oxamato-based dicopper(II) metallacyclophanes also emerge as potential candidates for the study of coherent electron transport through single molecules, both experimentally and theoretically. The results presented herein, which are a first step in the metallosupramolecular approach to molecular spintronics, intend to attract the attention of physicists and materials scientists with a large expertice in the manipulation and measurement of single-molecule electron transport properties, as well as in the processing and addressing of molecules on different supports.

Solid-State Molecular Nanomagnet Inclusion into a Magnetic Metal-Organic Framework: Interplay of the Magnetic Properties.

Single-ion magnets (SIMs) are the smallest possible magnetic devices and are a controllable, bottom-up approach to nanoscale magnetism with potential applications in quantum computing and high-density information storage. In this work, we take advantage of the promising, but yet insufficiently explored, solid-state chemistry of metal-organic frameworks (MOFs) to report the single-crystal to single-crystal inclusion of such molecular nanomagnets within the pores of a magnetic MOF. The resulting host-guest supramolecular aggregate is used as a playground in the first in-depth study on the interplay between the internal magnetic field created by the long-range magnetic ordering of the structured MOF and the slow magnetic relaxation of the SIM.

Two Polymorphic Forms of a Six-Coordinate Mononuclear Cobalt(II) Complex with Easy-Plane Anisotropy: Structural Features, Theoretical Calculations, and Field-Induced Slow Relaxation of the Magnetization.

A mononuclear cobalt(II) complex [Co(3,5-dnb)2(py)2(H2O)2] {3,5-Hdnb = 3,5-dinitrobenzoic acid; py = pyridine} was isolated in two polymorphs, in space groups C2/c (1) and P21/c (2). Single-crystal X-ray diffraction analyses reveal that 1 and 2 are not isostructural in spite of having equal formulas and ligand connectivity. In both structures, the Co(II) centers adopt octahedral {CoN2O4} geometries filled by pairs of mutually trans terminal 3,5-dnb, py, and water ligands. However, the structures of 1 and 2 disclose distinct packing patterns driven by strong intermolecular O-H···O hydrogen bonds, leading to their 0D→2D (1) or 0D→1D (2) extension. The resulting two-dimensional layers and one-dimensional chains were topologically classified as the sql and 2C1 underlying nets, respectively. By means of DFT theoretical calculations, the energy variations between the polymorphs were estimated, and the binding energies associated with the noncovalent interactions observed in the crystal structures were also evaluated. The study of the direct-current magnetic properties, as well as ab initio calculations, reveal that both 1 and 2 present a strong easy-plane magnetic anisotropy (D > 0), which is larger for the latter polymorph (D is found to exhibit values between +58 and 117 cm(-1) depending on the method). Alternating current dynamic susceptibility measurements show that these polymorphs exhibit field-induced slow relaxation of the magnetization with Ueff values of 19.5 and 21.1 cm(-1) for 1 and 2, respectively. The analysis of the whole magnetic data allows the conclusion that the magnetization relaxation in these polymorphs mainly takes place through a virtual excited state (Raman process). It is worth noting that despite the notable difference between the supramolecular networks of 1 and 2, they exhibit almost identical magnetization dynamics. This fact suggests that the relaxation process is intramolecular in nature and that the virtual state involved in the two-phonon Raman process lies at a similar energy in polymorphs 1 and 2 (∼20 cm(-1)). Interestingly, this value is recurrent in Co(II) single-ion magnets, even for those displaying different coordination number and geometry.

Dicopper(II) Metallacyclophanes with N,N'-2,6-Pyridinebis(oxamate): Solution Study, Synthesis, Crystal Structures, and Magnetic Properties.

The complexing ability of copper(II) in solution by the ligand N,N'-2,6-pyridinebis(oxamic acid) (H4mpyba, H4L) was determined through potentiometric and UV-vis spectroscopy at 25 °C and 0.15 M NaCl. The logarithms of the equilibrium constants for its copper(II) complexes according to the eqs 2H2L + 2Cu ⇆ [Cu2(H2L)2], 2H2L + 2Cu ⇆ [Cu2(H2L) (HL)] + H, 2H2L + 2Cu ⇆ [Cu2(HL)2] + 2H, 2H2L + 2Cu ⇆ [Cu2(HL)(L)] + 3H, and 2H2L + 2Cu ⇆ [Cu2L2] + 4H were 12.02(7), 8.04(5), 1.26(6), -7.51(6), and -16.36(6), respectively. The knowledge of the solution behavior has supported the synthesis of three new compounds bearing the common building block Cu2L2(4-). Their formulas are (Me4N)4[Cu2(mpyba)2(H2O)2]·H2O (1), (Me4N)4[K2Na2Cu4(mpyba)4(H2O)6.8]·1.6H2O (2), and [Na6Cu2(mpyba)2Cl2(H2O)8]·7H2O (3) (Me4N(+) = tetramethylammonium cation). The [Cu2(mpyba)2(H2O)2](4-) tetraanionic unit, which is present in 1, has a [3,3] metallacyclophane-type motif connected by two N-Cu-N bonds. In 2, a heterotrimetallic decanuclear nanocage is formed through front-to-front assembly of two [Cu2(mpyba)2](4-) units, which also coordinate to potassium(I) and sodium(I) cations by means of carboxylate oxygens from oxamate. The structure of 3 consists of heterobimetallic layers of formula [Na6Cu2(mpyba)2Cl2(H2O)8] and crystallization water molecules, which are interlinked by hydrogen bonds leading to a supramolecular three-dimensional network. The investigation of the magnetic properties of 1-3 in the temperature range 1.9-300 K shows the occurrence of ferromagnetic interactions between the dicopper(II) metallacyclophane unit [J = +6.85 (1), +7.40 (2), and +7.90 cm(-1) (3); H = -JSCu1·SCu2, where SCu1 = SCu2 = 1/2]. Theoretical calculations on 1-3 were carried to substantiate the nature and magnitude of the involved magnetic interactions and to support the occurrence of a spin polarization mechanism accounting for them.

The effect of crystal packing and Re(IV) ions on the magnetisation relaxation of [Mn6]-based molecular magnets.

The energy barrier to magnetisation relaxation in single-molecule magnets (SMMs) proffers potential technological applications in high-density information storage and quantum computation. Leading candidates amongst complexes of 3d metals ions are the hexametallic family of complexes of formula [Mn6 O2 (R-sao)6 (X)2 (solvent)y ] (saoH2 =salicylaldoxime; X=mono-anion; y=4-6; R=H, Me, Et, and Ph). The recent synthesis of cationic [Mn6 ][ClO4 ]2 family members, in which the coordinating X ions were replaced with non-coordinating anions, opened the gateway to constructing families of novel [Mn6 ] salts in which the identity and nature of the charge balancing anions could be employed to alter the physical properties of the complex. Herein we demonstrate initial experiments to show that this is indeed possible. By replacing the diamagnetic ClO4 (-) anions with the highly anisotropic Re(IV) ion in the form of [Re(IV) Cl6 ](2-) , the energy barrier to magnetisation relaxation is increased by up to 30 %.

Heterotrimetallic coordination polymers: {Cu(II)Ln(III)Fe(III)} chains and {Ni(II)Ln(III)Fe(III)} layers: synthesis, crystal structures, and magnetic properties.

The use of the [Fe(III) (AA)(CN)4](-) complex anion as metalloligand towards the preformed [Cu(II) (valpn)Ln(III)](3+) or [Ni(II) (valpn)Ln(III) ](3+) heterometallic complex cations (AA=2,2'-bipyridine (bipy) and 1,10-phenathroline (phen); H2 valpn=1,3-propanediyl-bis(2-iminomethylene-6-methoxyphenol)) allowed the preparation of two families of heterotrimetallic complexes: three isostructural 1D coordination polymers of general formula {[Cu(II) (valpn)Ln(III) (H2O)3 (µ-NC)2 Fe(III) (phen)(CN)2 {(µ-NC)Fe(III) (phen)(CN)3}]NO3 ⋅7 H2O}n (Ln=Gd (1), Tb (2), and Dy (3)) and the trinuclear complex [Cu(II) (valpn)La(III) (OH2 )3 (O2 NO)(µ-NC)Fe(III) (phen)(CN)3 ]⋅NO3 ⋅H2O⋅CH3 CN (4) were obtained with the [Cu(II) (valpn)Ln(III)](3+) assembling unit, whereas three isostructural heterotrimetallic 2D networks, {[Ni(II) (valpn)Ln(III) (ONO2 )2 (H2 O)(µ-NC)3 Fe(III) (bipy)(CN)]⋅2 H2 O⋅2 CH3 CN}n (Ln=Gd (5), Tb (6), and Dy (7)) resulted with the related [Ni(II) (valpn)Ln(III) ](3+) precursor. The crystal structure of compound 4 consists of discrete heterotrimetallic complex cations, [Cu(II) (valpn)La(III) (OH2)3 (O2 NO)(µ-NC)Fe(III) (phen)(CN)3 ](+), nitrate counterions, and non-coordinate water and acetonitrile molecules. The heteroleptic {Fe(III) (bipy)(CN)4} moiety in 5-7 acts as a tris-monodentate ligand towards three {Ni(II) (valpn)Ln(III)} binuclear nodes leading to heterotrimetallic 2D networks. The ferromagnetic interaction through the diphenoxo bridge in the Cu(II)-Ln(III) (1-3) and Ni(II)-Ln(III) (5-7) units, as well as through the single cyanide bridge between the Fe(III) and either Ni(II) (5-7) or Cu(II) (4) account for the overall ferromagnetic behavior observed in 1-7. DFT-type calculations were performed to substantiate the magnetic interactions in 1, 4, and 5. Interestingly, compound 6 exhibits slow relaxation of the magnetization with maxima of the out-of-phase ac signals below 4.0 K in the lack of a dc field, the values of the pre-exponential factor (τo) and energy barrier (Ea ) through the Arrhenius equation being 2.0×10(-12)  s and 29.1 cm(-1), respectively. In the case of 7, the ferromagnetic interactions through the double phenoxo (Ni(II)-Dy(III)) and single cyanide (Fe(III)-Ni(II)) pathways are masked by the depopulation of the Stark levels of the Dy(III) ion, this feature most likely accounting for the continuous decrease of χMT upon cooling observed for this last compound.

Field-Induced Slow Magnetic Relaxation in a Mononuclear Manganese(III)-Porphyrin Complex.

We report on a novel manganese(III)-porphyrin complex with the formula [Mn(III) (TPP)(3,5-Me2 pyNO)2 ]ClO4 ⋅CH3 CN (2; 3,5-Me2 pyNO=3,5-dimethylpyridine N-oxide, H2 TPP=5,10,15,20-tetraphenylporphyrin), in which the Mn(III) ion is six-coordinate with two monodentate 3,5-Me2 pyNO molecules and a tetradentate TPP ligand to build a tetragonally elongated octahedral geometry. The environment in 2 is responsible for the large and negative axial zero-field splitting (D=-3.8 cm(-1) ), low rhombicity (E/|D|=0.04) of the high-spin Mn(III) ion, and, ultimately, for the observation of slow magnetic-relaxation effects (Ea =15.5 cm(-1) at H=1000 G) in this rare example of a manganese-based single-ion magnet (SIM). Structural, magnetic, and electronic characterizations were carried out by means of single-crystal diffraction studies, variable-temperature direct- and alternating-current measurements and high-frequency and -field EPR spectroscopic analysis followed by quantum-chemical calculations. Slow magnetic-relaxation effects were also observed in the already known analogous compound [Mn(III) (TPP)Cl] (1; Ea =10.5 cm(-1) at H=1000 G). The results obtained for 1 and 2 are compared and discussed herein.

Cation Exchange in Dynamic 3D Porous Magnets: Improvement of the Physical Properties.

We report two novel three-dimensional porous coordination polymers (PCPs) of formulas Li4{Mn4[Cu2(Me3mpba)2]3}·68H2O (2) and K4{Mn4[Cu2(Me3mpba)2]3}·69H2O (3) obtained-via alkali cation exchange in a single-crystal to single-crystal process-from the earlier reported anionic manganese(II)-copper(II) PCP of formula Na4{Mn4[Cu2(Me3mpba)2]3}·60H2O (1) [Me3mpba(4-) = N,N'-2,4,6-trimethyl-1,3-phenylenebis(oxamate)]. This postsynthetic process succeeds where the direct synthesis in solution from the corresponding building blocks fails and affords significantly more robust PCPs with enhanced magnetic properties [long-range 3D magnetic ordering temperatures for the dehydrated phases (1'-3') of 2.0 (1'), 12.0 (2'), and 20.0 K (3')]. Changes in the adsorptive properties upon postsynthetic exchange suggest that the nature, electrostatic properties, mobility, and location of the cations within the framework are crucial for the enhanced structural stability. Overall, these results further confirm the potential of postsynthetic methods (including cation exchange) to obtain PCPs with novel or enhanced physical properties while maintaining unaltered their open-framework structures.

Dicopper(II) anthraquinophanes as multielectron reservoirs for oxidation and reduction: a joint experimental and theoretical study.

Two new dinuclear copper(II) metallacyclophanes with 1,4-disubstituted 9,10-anthraquinonebis(oxamate) bridging ligands are reported that can reversibly take and release electrons at the redox-active ligand and metal sites, respectively, to give the corresponding mono- and bis(semiquinonate and/or catecholate) Cu(II)2 species and mixed-valent Cu(II)/Cu(III) and high-valent Cu(III)2 ones. Density functional calculations allow us to give further insights on the dual ligand- and metal-based character of the redox processes in this novel family of antiferromagnetically coupled di- copper(II) anthraquinophanes. This unique ability for charge storage could be the basis for the development of new kinds of molecular spintronic devices, referred to as molecular magnetic capacitors (MMCs).

How the spin state tunes the slow magnetic relaxation field dependence in spin crossover cobalt(II) complexes.

A novel family of cobalt(II) compounds with tridentate pyridine-2,6-diiminephenyl type ligands featuring electron-withdrawing substituents of general formula [Co(n-XPhPDI)2](ClO4)2·S [n-XPhPDI = 2,6-bis(N-n-halophenylformimidoyl)pyridine with n = 4 (1-3) and 3 (4); X = I (1), Br (2 and 4) and Cl (3); S = MeCN (1 and 2) and EtOAc (3)] has been synthesised and characterised by single-crystal X-ray diffraction, electron paramagnetic resonance, and static (dc) and dynamic (ac) magnetic measurements combined with theoretical calculations. The structures of 1-4 consist of mononuclear bis(chelating) cobalt(II) complex cations, [CoII(n-XPhPDI)2]2+, perchlorate anions, and acetonitrile (1 and 2) or ethyl acetate (3) molecules of crystallisation. This unique series of mononuclear six-coordinate octahedral cobalt(II) complexes displays both thermally-induced low-spin (LS)/high-spin (HS) transition and field-induced slow magnetic relaxation in both LS and HS states. A complete LS ↔ HS transition occurs for 1 and 2, while it is incomplete for 4, one-third of the complexes being HS at low temperatures. In contrast, 3 remains HS in all the temperature range. 1 and 2 show dual spin relaxation dynamics under the presence of an applied dc magnetic field (Hdc), with the occurrence of faster- (FR) and slower-relaxing (SR) processes at lower (Hdc = 1.0 kOe) and higher fields (Hdc = 2.5 kOe), respectively. On the contrary, 3 and 4 exhibit only SR and FR relaxations, regardless of Hdc. Overall, the distinct field-dependence of the single-molecule magnet (SMM) behaviour along with this family of spin-crossover (SCO) cobalt(II)-n-XPhPDI complexes is dominated by Raman mechanisms and, occasionally, with additional temperature-independent Intra-Kramer [LS or HS (D > 0)] or Quantum Tunneling of Magnetisation mechanisms [HS (D < 0)] also contributing.