Elevating the Performance of Heterometallic 3d/4f SMMs: The Role of Diamagnetic CoIII and ZnII Ions in Magnetization Dynamics.

Recent advances in the synthesis of 3d/4f Single-Molecule Magnets (SMMs) have revealed the effective role of incorporating diamagnetic CoIII or ZnII ions to enhance the magnetic properties of LnIII ions. This concept highlights notable examples of CoIII/LnIII and ZnII/LnIII SMMs documented in the recent literature, illustrating how the selection of various peripheral and/or bridging ligands can modulate the magnetic anisotropy of 4f metal ions, thereby increasing their energy barriers.

Slow Magnetization Relaxation in a Family of Triangular {CoIII 2 LnIII } Clusters: The Effect of Diamagnetic CoIII Ions on the LnIII Magnetic Dynamics.

The first use of the Schiff base chelate N-naphthalidene-o-aminophenol (naphH2 ) in Co/Ln chemistry has afforded a family of isostructural [CoIII 2 LnIII (OMe)2 (naph)2 (O2 CMe)3 (MeOH)2 ] (Ln=Tb, Dy and Er) complexes, revealing a rare {CoIII 2 Ln(µ3 -OMe)}8+ triangular core composed of two diamagnetic CoIII ions and a 4f-ion with slightly distorted square antiprismatic geometry. Alternating current (ac) magnetic susceptibility studies revealed that {Co2 Dy}, and its magnetic diluted analogue {Co2 Dy0.05 Y0.95 }, behave as mononuclear single-molecule magnets (SMMs) with similar energy barriers for the magnetization reversal, Ueff , of ~85-90 K. SMM properties were also detected for {Co2 Er}, with the compound exhibiting a Ueff of 18.7 K under an applied magnetic field of 800 Oe. To interpret the experimental magnetic results, ab initio CASSCF/RASSI-SO and DFT calculations were performed as a means of exploring the single-ion characteristics of LnIII ions and comprehend the role of the diamagnetic CoIII ions in the magnetization relaxation of the three heterometallic compounds.

4f-Metal Clusters Exhibiting Slow Relaxation of Magnetization: A {Dy7} Complex with An Hourglass-like Metal Topology.

The reaction between Dy(NO3)3∙6H2O and the bulky Schiff base ligand, N-naphthalidene-2-amino-5-chlorobenzoic acid (nacbH2), in the presence of the organic base NEt3 has led to crystallization and structural, spectroscopic and magnetic characterization of a new heptanuclear [Dy7(OH)6(OMe)2(NO3)1.5(nacb)2(nacbH)6(MeOH)(H2O)2](NO3)1.5 (1) compound in ~40% yield. Complex 1 has a unique hourglass-like metal topology, among all previously reported {Dy7} clusters, comprising two distorted {Dy4(µ3-OH)3(µ3-OMe)}8+ cubanes that share a common metal vertex (Dy2). Peripheral ligation about the metal core is provided by the carboxylate groups of four η1:η1:η1:µ single-deprotonated nacbH- and two η1:η1:η2:η1:µ3 fully-deprotonated nacb2- ligands. Complex 1 is the first structurally characterized 4f-metal complex bearing the chelating/bridging ligand nacbH2 at any protonation level. Magnetic susceptibility studies revealed that 1 exhibits slow relaxation of magnetization at a zero external dc field, albeit with a small energy barrier of ~5 K for the magnetization reversal, most likely due to the very fast quantum-tunneling process. The combined results are a promising start to further explore the reactivity of nacbH2 upon all lanthanide ions and the systematic use of this chelate ligand as a route to new 4f-metal cluster compounds with beautiful structures and interesting magnetic dynamics.

Structural and Magnetic Variations in a Family of Isoskeletal, Oximate-Bridged {MnIV2 MIII } Complexes (MIII =Mn, Gd, Dy).

The self-assembly reaction of MnCl2 ⋅4H2 O, acenaphthenequinone dioxime (acndH2 ) and NEt3 has yielded an unprecedented, linear {MnIV2 MnIII } complex with an S=5 spin ground state and non-SMM behavior. The targeted replacement of the central MnIII ion with GdIII and DyIII ions has successfully increased the S and turned on the SMM dynamics without affecting the core structure and the nature of the magnetic exchange interactions.

Oximato-Based Ligands in 3 d/4 f-Metal Cluster Chemistry: A Family of {Cu3Ln} Complexes with a "Propeller"-like Topology and Single-Molecule Magnetic Behavior.

The organic chelating and bridging ligands 9,10-phenanthrenedione-9-oxime (phenoxH) and 9,10-phenanthrenedione-9,10-dioxime (phendoxH2) were synthesized and subsequently employed for the first time in heterometallic 3 d/4 f-metal cluster chemistry. The general reaction between CuCl2·2H2O, LnCl3·6H2O, phenoxH, and NEt3 in a 1:2:2:4 molar ratio, in a solvent mixture comprising MeCN and MeOH, afforded brown crystals of a new family of [Cu3LnCl3(phenox)6(MeOH)3] clusters (Ln = Gd (1), Tb (2), Dy (3)) that possess an unprecedented [Cu3Ln(µ-NO)6]3+ "propeller"-like core. Complexes 1-3 are the first {Cu3Ln} clusters in which the outer CuII and the central LnIII atoms are solely bridged by diatomic oximato bridges. The {Cu-N-O-Ln} bridging units are very distorted with torsion angles spanning the range 35.5-48.9° and 25.2-55.6° in 1 and 2, respectively. As a result, complexes 1-3 are antiferromagnetically coupled, in agreement with previously reported magnetostructural criteria for oximato-bridged Cu/Ln complexes. The magnetic susceptibility data for all complexes were nicely fit to an isotropic spin Hamiltonian (for 1) or a Hamiltonian that accounts for the spin of the CuII atoms, the spin component of the LnIII, the spin-orbit coupling (λ), an axial ligand-field component around the LnIII atoms (Δ), and the Zeeman effect (for the anisotropic 2 and 3). The resulting fit parameters were J = -1.34 cm-1 and g = 2.10 (1), J = -1.42 cm-1, gCu = 2.10, and Δ = -26.3 cm-1 (2), and J = -1.70 cm-1, gCu = 2.05, and Δ = -38.1 cm-1 (3). The reported fitting procedure, implemented in the PHI program, is here used for the first time. Even if this method is only valid in high-symmetry Ln environments, when it is properly used allows a very simple and efficient method to obtain the exchange parameters. In light of the negative anisotropy, compounds 2 and 3 were found to exhibit frequency-dependent tails of out-of-phase signals in the presence of a small external dc field, characteristic of the slow magnetization relaxation of a single-molecule magnet. By using the Kramers-Kronig equations, the effective energy barriers ( Ueff) were derived and reported as Ueff = 10.1 and 5.4 cm-1 for 2 and 3, respectively.

Transition Metal Single-Molecule Magnets: A {Mn31} Nanosized Cluster with a Large Energy Barrier of ∼60 K and Magnetic Hysteresis at ∼5 K.

The first {Mn31} cluster (1) has been prepared from carboxylate ions and the chelating/bridging ligand α-methyl-2-pyridine-methanol. Compound 1 possesses a unique nanosized structural topology with one of the largest energy barriers reported to-date for high-nuclearity 3d-metal clusters. Single-crystal magnetic hysteresis studies reveal the presence of hysteresis loops below 5 K, one of the highest temperatures below which molecular hysteresis has been observed for 3d-based SMMs.

Large Energy Barrier and Magnetization Hysteresis at 5 K for a Symmetric {Dy2} Complex with Spherical Tricapped Trigonal Prismatic DyIII Ions.

The introduction of the Schiff base ligand N-salicylidene-2-amino-5-chlorobenzoic acid (sacbH2) in 4f-metal chemistry has afforded a new dinuclear complex, [Dy2(NO3)4(sacbH)2(H2O)2(MeCN)2] (1), with the metal ions adopting a rare spherical tricapped trigonal prismatic coordination geometry. The deprotonated phenoxido O atoms of the organic chelate occupy the axial triangular faces of the prism and were found to be very close to the main anisotropy axes of the two DyIII ions. As a result, the {DyIII2} compound exhibits frequency- and temperature-dependent out-of-phase ac signals below ∼25 K in the absence of a static dc field, yielding an energy barrier of 109.3(1) K for the reversal of magnetization. Fast and efficient quantum tunneling of magnetization, attributed to the strong tails of signals below ∼15 K, was suppressed through the application of a small dc field, yielding entirely visible χM″ signals below 27 K. Single-crystal magnetic hysteresis studies confirmed the single-molecule magnet (SMM) behavior of 1; the hysteresis loops appear at temperatures below ∼5 K, which is one of the highest blocking temperatures in the field of 4f-SMMs to date. This joint magneto-structural and ab initio study demonstrates the ability of more common coordination numbers (i.e., 9), but with rare coordination geometries (i.e., spherical tricapped trigonal prismatic), to promote axiality that enhances the molecular anisotropy and subsequently the magnetization dynamics of the system.

Structural Diversities in Heterometallic Mn-Ca Cluster Chemistry from the Use of Salicylhydroxamic Acid: {MnIII4Ca2}, {MnII/III6Ca2}, {MnIII/IV8Ca}, and {MnIII8Ca2} Complexes with Relevance to Both High- and Low-Valent States of the Oxygen-Evolving Complex.

One-pot reactions between the [Mn3O(O2CPh)6(py)x]+/0 triangular precursors and either CaBr2·xH2O or CaCl2·6H2O, in the presence of salicylhydroxamic acid (shaH2), have afforded the heterometallic complexes [MnIII4Ca2(O2CPh)4(shi)4(H2O)3(Me2CO)] (1) and (pyH)[MnII2MnIII4Ca2Cl2(O2CPh)7(shi)4(py)4] (2), respectively, in good yields. Further reactions but using a more flexible synthetic scheme comprising the Mn(NO3)2·4H2O/Ca(NO3)2·4H2O and Mn(O2CPh)2·2H2O/Ca(ClO4)2·4H2O "metal blends" and shaH2, in the presence of external base NEt3, led to the new complexes (NHEt3)2[MnIII4MnIV4Ca(OEt)2(shi)10(EtOH)2] (3) and (NHEt3)4[MnIII8Ca2(CO3)4(shi)8] (4), respectively. In all reported compounds, the anion of the tetradentate (N,O,O,O)-chelating/bridging ligand salicylhydroxime (shi3-), resulting from the in situ metal-ion-assisted amide-iminol tautomerism of shaH2, was found to bridge both Mn and Ca atoms. Complexes 1-4 exhibit a variety of different structures, metal stoichiometries, and Mn oxidation-state descriptions; 1 possesses an overall octahedral metal arrangement, 2 can be described as a Mn4Ca2 octahedron bound to an additional Mn2 unit, 3 consists of a Mn8 "ring" surrounding a CaII atom, and 4 adopts a rectangular cuboidal motif of eight Mn atoms accommodating two CaII atoms. Solid-state direct-current magnetic susceptibility studies revealed the presence of predominant antiferromagnetic exchange interactions between the Mn centers, leading to S = 0 spin ground-state values for all complexes. From a bioinorganic chemistry perspective, the reported compounds may demonstrate some relevance to both high-valent scheme (3) and lower-oxidation-level species (1, 2, and 4) of the catalytic cycle of the oxygen-evolving complex.

"Molecular Nanoclusters": A 2-nm-Sized {Mn29} Cluster with a Spherical Structure.

The comproportionation reaction between MnII and MnVII sources in the presence of 3,3-dimethylacrylic acid and azides has led to a new {Mn29} molecular cluster with a spherical structure and dimensions of ∼2.2 nm, comparable in size to the smallest classical and magnetic nanoparticles.

"Ligands-with-Benefits": Naphthalene-Substituted Schiff Bases Yielding New Ni(II) Metal Clusters with Ferromagnetic and Emissive Properties and Undergoing Exciting Transformations.

The initial employment of the fluorescent bridging ligand N-naphthalidene-2-amino-5-chlorobenzoic acid (nacbH2) in metal cluster chemistry has led to new Ni12 (1) and Ni5 (2) clusters with wheel-like and molecular-chain topologies, respectively. The doubly-deprotonated nacb(2-) ligands were found to adopt four different coordination modes within 1 and 2. The nature of the ligand has also allowed unexpected organic transformations to occur and ferromagnetic and emission behaviors to emerge. The combined work demonstrates the ability of some "ligands-with-benefits" to yield beautiful structures with exciting topologies and interesting physicochemical properties.

Emissive {Mn4(III)Ca} clusters with square pyramidal topologies: syntheses and structural, spectroscopic, and physicochemical characterization.

The one-pot reactions between Mn(ClO4)2·6H2O, Ca(ClO4)2·4H2O, and the potentially tetradentate (N,O,O,O) chelating/bridging ligand salicylhydroxime (shiH3), resulting from the in situ metal ion-assisted amide-iminol tautomerism of salicylhydroxamic acid in the presence of various fluorescence carboxylate groups and base NEt3, afford a family of structurally similar {Mn4Ca} clusters with distorted square pyramidal topology. The reported complexes (NHEt3)2[Mn4Ca(L1)4(shi)4] (1), (NHEt3)2[Mn4Ca(L2)4(shi)4] (2), (NHEt3)5[Mn4Ca(L2)4(shi)4(shiH2)2](ClO4) (3), and (NHEt3)2[Mn4Ca(L3)4(shi)4] (4) contain a similar [Mn4Ca(µ-NO)4](10+) core of four Mn(III) atoms at the square base and a Ca(II) atom occupying the apical site. Peripheral ligation about the core is provided by four η(1):η(1):µ carboxylate groups of the anions of 2-naphthoic acid (L1(-)), 9-anthracenecarboxylic acid (L2(-)), and 1-pyrenecarboxylic acid (L3(-)). Solid-state direct current magnetic susceptibility studies revealed the presence of predominant antiferromagnetic exchange interactions between the 4 Mn(III) centers, which were primarily quantified by using a simple 1-J fit model to give S = 0 spin ground states with low-lying excited states close in energy to the ground state. Solution studies in solvent MeCN were carried out on all complexes and confirmed their structural integrity. Cyclic voltammetry studies showed a similar well-defined reversible oxidation and an irreversible reduction for all complexes, thus establishing their redox potency and electrochemical efficiency. Emission studies in solution proved the optical activity of all compounds, with the observed "blue" emission peaks attributed to the π-rich chromophores of the organic fluorescence ligands. The combined results demonstrate the ability of shiH3 and fluorescence carboxylates to yield new heterometallic Mn/Ca clusters with (i) the same Mn/Ca ratio as the oxygen-evolving complex of Photosystem II, (ii) structural stability in solution, and (iii) a pronounced redox and optical activity.

Nonemployed Simple Carboxylate Ions in Well-Investigated Areas of Heterometallic Carboxylate Cluster Chemistry: A New Family of {Cu(II)4Ln(III)8} Complexes Bearing tert-Butylacetate Bridging Ligands.

The first use of tert-butylacetate as bridging ligand in 3d/4f-metal cluster chemistry, in conjunction with the versatile chelate ligand pyridine-2,6-dimethanol, has afforded a new family of [Cu4Ln8(OH)6(NO3)2(O2CCH2Bu(t))16(pdm)4] clusters with unprecedented structures and slow magnetization relaxation for the {Cu(II)4Dy(III)8} member. The molecular structure of representative complex 1 consists of a {Cu(II)4Gd(III)8} cage-like cluster built from two {CuGd3} cubanes which are linked to each other and to two {CuGd} subunits on opposite sides through two η(2):η(2):η(2):µ5 NO3(-) ions. The metal ions are additionally bridged by µ3-OH(-), µ3-OR(-), and µ-OR(-) groups to give an overall [Cu4Gd8(µ5-NO3)2(µ3-OH)6(µ3-OR)2(µ-OR)8](14+) core. Peripheral ligation about the core is provided by the N,O,O-chelating part of the pdm(2-) groups and, more impressively, by the oxygen atoms of 16 bridging Bu(t)CH2CO2(-) ligands; the latter are arranged into five classes, adopting a total of six different binding modes with the metal centers. The combined work demonstrates the ligating flexibility of tert-butylacetate ion and its usefulness in the synthesis of new 3d/4f-metal cluster compounds.

Synthetic model of the asymmetric [Mn3CaO4] cubane core of the oxygen-evolving complex of photosystem II.

The laboratory synthesis of the oxygen-evolving complex (OEC) of photosystem II has been the objective of synthetic chemists since the early 1970s. However, the absence of structural information on the OEC has hampered these efforts. Crystallographic reports on photosystem II that have been appearing at ever-improving resolution over the past ten years have finally provided invaluable structural information on the OEC and show that it comprises a [Mn(3)CaO(4)] distorted cubane, to which is attached a fourth, external Mn atom, and the whole unit attached to polypeptides primarily by aspartate and glutamate carboxylate groups. Such a heterometallic Mn/Ca cubane with an additional metal attached to it has been unknown in the literature. This paper reports the laboratory synthesis of such an asymmetric cubane-containing compound with a bound external metal atom, [(1)]. All peripheral ligands are carboxylate or carboxylic acid groups. Variable-temperature magnetic susceptibility data have established 1 to possess an S = 9/2 ground state. EPR spectroscopy confirms this, and the Davies electron nuclear double resonance data reveal similar hyperfine couplings to those of other Mn(IV) species, including the OEC S(2) state. Comparison of the X-ray absorption data with those for the OEC reveal 1 to possess structural parameters that make it a close structural model of the asymmetric-cubane OEC unit. This geometric and electronic structural correspondence opens up a new front in the multidisciplinary study of the properties and function of this important biological unit.

New classes of ferromagnetic materials with exclusively end-on azido bridges: from single-molecule magnets to 2 D molecule-based magnets.

A new, flexible synthetic route, which does not require the co-presence of any organic chelating/bridging ligand but only the "key" precursor Me3SiN3, has been discovered and led to a new class of inorganic materials containing exclusively end-on azido bridges; the reported 3d-metal clusters and coordination polymers exhibit ferromagnetic, single-molecule magnet, and long-range magnetic ordering properties.

Tetranuclear lanthanide(III) complexes with a zigzag topology from the use of pyridine-2,6-dimethanol: synthetic, structural, spectroscopic, magnetic and photoluminescence studies.

Reaction between Ln(NO3)3·xH2O (x = 5 or 6) and the potentially tridentate (N,O,O) chelating/bridging ligand pyridine-2,6-dimethanol (pdmH2), in the presence of base NEt3, affords a family of isostructural tetranuclear [Ln(III)4(NO3)2(pdmH)6(pdmH2)2](NO3)4 (Ln(III) = Eu(III), Gd(III), Tb(III), Dy(III), Ho(III), Er(III), Yb(III)) complexes with a rare zigzag topology. All complexes contain a [Ln4(µ-OR)6](6+) core with bridging ligation provided by the alkoxido arms of six η(1):η(1):η(2):µ pdmH(-) groups. The Ln(III) ions are eight coordinate with distorted geometries. Direct current magnetic susceptibility studies revealed predominant weak antiferromagnetic exchange interactions between the metal centers, which were quantified in the case of isotropic Gd(III)4 to give J = -0.09(1) cm(-1) and g = 2.00(1). The observation of out-of-phase (χ″M) ac susceptibility signals suggested that the Dy(III)4 analogue might be a molecular nanomagnet. Solid-state photoluminescence studies showed that the Eu(III)4 and Tb(III)4 compounds exhibit intense, sharp, and narrow emission bands in the red and green visible regions, respectively, which arise from the characteristic (5)D0 → (7)FJ and (5)D4 → (7)FJ transitions. The combined results demonstrate the ability of pdmH2 ligand to yield homometallic 4f clusters with interesting magnetic and optical properties.

Fluorescent naphthalene diols as bridging ligands in Ln(III) cluster chemistry: synthetic, structural, magnetic, and photophysical characterization of Ln(III)8 "Christmas stars".

The initial employment of the fluorescent bridging ligand naphthalene-2,3-diol in 4f-metal coordination chemistry has provided access to a new family of Ln(III)8 clusters with a "Christmas-star" topology, single-molecule magnetism behavior, and ligand-centered emissions.

Unveiling new [1+1] Schiff-base macrocycles towards high energy-barrier hexagonal bipyramidal Dy(III) single-molecule magnets.

The employment of the [1+1] condensation approach for the preparation of new macrocyclic scaffolds (LN6 and LN3O3) towards high-performance Dy(III) single-molecule magnets (SMMs) with pseudo-D6h symmetry is described. Engineering of the macrocycles denticity from LN6 to LN3O3 leads to a mononuclear SMM with a large Ueff value of 1300 K. The experimental results are supported by ab initio calculations, which indicate relaxation of the magnetization via the second-excited state.

Molecular nanoscale magnetic refrigerants: a ferrimagnetic {Cu(II)15Gd(III)7} cagelike cluster from the use of pyridine-2,6-dimethanol.

The employment of pyridine-2,6-dimethanol in 3d/4f metal cluster chemistry has afforded a new {Cu(II)15Gd(III)7} cagelike molecule with a beautiful structure built by fused triangular subunits; the compound exhibits an overall ferrimagnetic behavior with an appreciable ground-state spin value and shows promise as a low-temperature magnetic refrigerant.

A MnII6MnIII6 single-strand molecular wheel with a reuleaux triangular topology: synthesis, structure, magnetism, and DFT studies.

The use of the anion of 3-methyl-1,3,5-pentanetriol (mpt(3-)) in manganese carboxylate chemistry has afforded the new Mn(II/III)12 cluster [Mn(II)6Mn(III)6(mpt)6(CH3CO2)12(py)6]·3CH3CN (1·3CH3CN). Complex 1 was isolated in moderate yield by the reaction of Mn(CH3CO2)2·4H2O and H3mpt in a 2.6:1 molar ratio in a solvent mixture of acetonitrile and pyridine. The structure of 1 consists of alternating [Mn(II)2(CH3CO2)3(py)](+) and [Mn(III)2(µ-OR)2(CH3CO2)(py)](3+) dimeric units (three of each dimer), linked at each end by two alkoxo and one acetate bridges; the mpt(3-) ligands adopt the η(2):η(2):η(2):µ4 coordination mode. The overall metal topology of this new Mn12 wheel resembles a guitar plectrum, or a Reuleaux triangle. Complex 1 displays an unprecedented structural topology, being the first example of a Mn(II)6Mn(III)6 wheel constructed from alternating homovalent dimers and the only known Mn12 loop with the trigonal symmetry of a Reuleaux triangle (all other reported loops were ellipsoids). Variable-temperature, solid-state direct- and alternating-current magnetization studies were carried out on complex 1, revealing the presence of antiferromagnetic exchange interactions between the metal ions in the molecule, which lead to a spin ground-state value S = 0; the exchange coupling parameters J were calculated using density functional theory employing a hybrid B3LYP functional.

2-Pyrrolyloximes in high-nuclearity transition-metal cluster chemistry: Fe10 and Fe12.

The employment of 2-pyrrolyloximes in high-nuclearity transition-metal cluster chemistry has provided access to unprecedented decanuclear and dodecanuclear Fe(III) cagelike clusters bearing the anion of pyrrole-2-carboxaldehyde oxime (praoH(2)), the simplest member of this new family of ligands; the identity of the products depends on the nature of the counteranion present in the starting materials.