Slow Magnetic Relaxation in Silver(II) Macrocyclic Systems.

The spin-lattice relaxation time has been studied trough alternating-current susceptometry and ultralow-frequency Raman spectroscopy in a family of silver(II)-derived molecular systems with spin 1/2 and formulas [AgII(m-CTH)(NO3)2] (1) and [AgII(m-CTH)(ClO4)2] (2), where CTH = meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane. The combination of both techniques demonstrates the occurrence of slow spin magnetic relaxation induced by spin-phonon interaction. The magnetic behavior of these silver(II)-derived systems opens the door to a new cation in the scarce family of S = 1/2 systems with slow relaxation of magnetization.

Single-Ion Anisotropy and Intramolecular Interactions in CeIII and NdIII Dimers.

This article reports the syntheses, characterization, structural description, together with magnetic and spectroscopic properties of two isostructural molecular magnets based on the chiral ligand N,N'-bis((1,2-diphenyl-(pyridine-2-yl)methylene)-(R,R/S,S)-ethane-1,2-diamine), L1, of general formula [Ln2(RR-L1)2(Cl6)]·MeOH·1.5H2O, (Ln = Ce (1) or Nd (2)). Multifrequency electron paramagnetic resonance (EPR), cantilever torque magnetometry (CTM) measurements, and ab initio calculations allowed us to determine single-ion magnetic anisotropy and intramolecular magnetic interactions in both compounds, evidencing a more important role of the anisotropic exchange for the NdIII derivative. The comparison of experimental and theoretical data indicates that, in the case of largely rhombic lanthanide ions, ab initio calculations can fail in determining the orientation of the weakest components, while being reliable in determining their principal values. However, they remain of paramount importance to set the analysis of EPR and CTM on sound basis, thus obtaining a very precise picture of the magnetic interactions in these systems. Finally, the electronic structure of the two complexes, as obtained by this approach, is consistent with the absence of zero-field slow relaxation observed in ac susceptibility.

Exploring the Role of Intramolecular Interactions in the Suppression of Quantum Tunneling of the Magnetization in a 3d-4f Single-Molecule Magnet.

Hydroxide-bridged FeIII4LnIII2 clusters having the general formula [Fe4Ln2(µ3-OH)2(mdea)6(SCN)2(NO3)2(H2O)2]·4H2O·2MeCN {Ln = Y (1), Dy (2), mdea = N-methyldiethanolamine} were synthesized and magnetically characterized. The thermal relaxation of the magnetization for 2 and the diluted FeIII4DyIIIYIII complex 3 (with and without applied field) has been analyzed. The diluted sample shows a dominant QTM at low temperatures that can be removed with a 0.15 T dc field. Both 2 and 3 show moderately high Ueff barriers and exhibit hysteresis loops until 5 K.

From Bowls to Capsules: Assembly of Hexanuclear NiII Rings Tailored by Alkali Cations.

An anionic hexanuclear NiII metallamacrocycle with endo and exo linking sites has been employed as a building block to generate a series of capsules and bowls of nanometric size. The supramolecular arrangement of the {Ni6 } rings was tailored by the size of the alkali cations, showing the transition from {Ni6 -M2 -Ni6 } capsules (M=LiI and NaI ) to {Ni6 -M} bowls (M=KI and CsI ). The alkyl co-cations are determinant to stabilize the assemblies by means of CH⋅⋅⋅π interactions on the exo side of the metallamacrocycles. The effect on the topology of the supramolecular assemblies of the cation size, cation charge, Et3 NH+ or Me4 N+ counter cations has been analyzed. Magnetic measurements reveal the presence of ferromagnetic and antiferromagnetic interactions inside the rings that allow a S=0 ground state.

Chiral Versus Non-Chiral [MnIII 6 MnII NaI ], [MnIII 6 MnII 2 NaI 2 ] and [MnIII 3 MnII NaI ] Clusters Derived from Schiff Bases or the Fight for Symmetry.

The reaction in basic media of manganese chloride with Schiff bases derived from the condensation of o-vanillin with different chiral/racemic aminoalcohols yielded in a family of complexes in which the nuclearity, symmetry and magnetic behavior is controlled by changing the position of the chiral carbon. Chiral and racemic clusters with [MnIII 6 MnII NaI ], [MnIII 6 MnII 2 NaI 2 ] and [MnIII 3 MnII NaI ] metallic core have been structurally and magnetically characterized. The racemic clusters with an odd number of chiral ligands exhibit the anomalous mixing of ligands with different conformation. Related racemic compounds have been reviewed.

Multifunctionality in Two Families of Dinuclear Lanthanide(III) Complexes with a Tridentate Schiff-Base Ligand.

The employment of N-(2-carboxyphenyl)salicylideneimine in 4f metal chemistry has led to two families of dinuclear complexes depending on the lanthanide(III) used. Representative members exhibit interesting magnetic, optical, and catalytic properties.

Chiral [MnII MnIII 3 M'] (M'=NaI , CaII , MnII ) and [MnII MnIII 6 NaI 2 ] Clusters Built from an Enantiomerically Pure Schiff Base: Synthetic, Chiroptical, and Magnetic Properties.

From the reaction of manganese halides with the chiral Schiff bases obtained by condensation of o-vanillin and (R)- or (S)-phenylglycinol, 11 complexes based on pentanuclear cages with trigonal bipyramidal [MnII MnIII 3 M'] (M'=NaI , CaII , MnII ) or enneanuclear [MnII MnIII 6 NaI 2 ] cores were synthesized. Structural, supramolecular chirality, and optical properties were explored. The magnetic properties of related systems were reviewed, and the magnetic response of the new systems was rationalized to the bond parameters.

From Mesocates to Helicates: Structural, Magnetic and Chiro-Optical Studies on Nickel(II) Supramolecular Assemblies Derived from Tetradentate Schiff Bases.

The systematic reactions of a family of tetradentate pyridyl/imine and quinolyl/imine racemic or enantiopure Schiff bases with Ni(NO3 )2 or Ni(ClO4 )2 in the presence of sodium azide yielded, as a function of the starting racemic, chiral or achiral base, a set of chiral, meso or achiral complexes. In all cases, the compounds consist of two NiII cations linked by a double azido bridge in its end-on coordination mode. All the dimers exhibit a mesocate supramolecular structure and one of them, the unprecedented mix of helicate and mesocate in 2:1 ratio. The transition from mesocate to helicate conformation has been reached by tuning the flexibility of the central spacers of the Schiff bases and the size of the substituents. Electronic circular dichroism (ECD) studies have been performed for two pairs of enantiomers and interpreted by means of DFT calculations. Susceptibility measurements show a ferromagnetic coupling between the NiII cations mediated by the end-on azido bridges.

Triple Halide Bridges in Chiral MnII2MnIII6NaI2 Cages: Structural and Magnetic Characterization.

A family of decanuclear chiral clusters with a MnII2MnIII6NaI2 core have been synthesized from enantiomerically pure Schiff bases. The new systems consist of two MnIIMnIII3NaI units linked by rare triple chloro or bromo bridges between the divalent Mn cations. Susceptibility measurements point out the weak antiferromagnetic interaction mediated by these kinds of bridges and afford the first magnetic measurements for the (µ-Br)3 case.

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.

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.

Linked Nickel Metallacrowns from a Phosphonate/2-Pyridyloximate Blend of Ligands: Structure and Magnetic Properties.

In the present work, four new Ni(II) clusters with nuclearities ranging between Ni4 and Na2Ni8 were synthesized, employing the versatile ligand phenylphosphonate and 6-methylpyridylaldoximate as the coligand. Crystallographic data show that the tetranuclear complex [Ni4(6-MepaoH)4(PhPO3)2(OH)2(MeOH)4](OH)2 (1) consists of two dimers linked by phosphonate bridges, whereas [Cs2Ni6(6-Mepao)6(PhPO3)3(OH)2(H2O)8] (2), Cs[Ni8(6-MepaoH)6(6-Mepao)6(PhPO3)3](ClO4)5 (3), and [Ni8Na2(BzO)6(6-Mepao)6(PhPO3)3] (4) are built from phosphonato-linked {Ni3(6-Mepao)3} metallacycles. The [9-MC(Ni(II)(6-Mepao))-3] fragments in 2-4 show the unusual coordination of additional Cs(+), Na(+), and/or Ni(II) cations. Direct-current magnetic measurements were carried in the 300-2 K range. Analysis of the experimental data revealed a complex response with strong antiferromagnetic interactions mediated by the oximato bridges and weak interactions mediated by the phosphonate ones.

"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.

Mn(II)- and Co(II)-Catalyzed Transformation of 2-Cyanopyrimidine to Methylimidate by Sodium Azide: Isolation, Structural Characterization, and Magnetic Studies on 2D Mn(II)- and Cu(II)-Complexes.

The Mn(II)-mediated transformation of 2-cyanopyrimidine to methylimidate in the presence of inorganic azide is proven through isolation and structural characterization of a metal complex. Though the reaction conditions are favorable for a "click" reaction leading to the formation of tetrazole, as evidenced from recent studies, we are astonished to see the formation of methylimidate in MeOH instead of tetrazole, which is supposed to form only in the presence of catalytic amount of corresponding alkoxide ion as base. The catalytic nature of this transformation reaction was confirmed by performing these experiments under catalytic conditions and analyzing the products using liquid chromatography-mass spectrometry techniques, which clearly showed ∼96% and ∼60% selectivity of methylimidate along with almost 100% conversion in the presence of Mn(II) and Co(II) as catalysts, respectively. In absence or presence of other metal ions like Cu(II), Ni(II), Fe(II), Zn(II), etc. only tetrazole formation takes place. So the present findings extended the formation of methylimidate catalyzed by metal ions in the presence of azide ion in alcoholic medium. Importantly, a probable mechanism for this unexpected transformation was framed based on the structural analysis and high-resolution mass spectrometry (electrospray ionization MS(+)) studies. The magnetic studies were also performed on complexes [Mn(L)(N3)2]n (1) and [Cu (L(2))2]n (2a), showing anti-ferromagnetic character for compound 1 and negligible coupling for the copper complex 2a.

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.

Ni(II)20 "Bowls" from the Use of Tridentate Schiff Bases.

The reactions of N-salicylidene-o-aminophenol or its derivatives and excess of nickel(II) acetate in alcohols have led to Ni(II)20 clusters with an unprecedented "bowl" metal topology.

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.

Anionic guests in prismatic cavities generated by enneanuclear nickel metallacycles.

The combination of polydentate aminated ligands with the 2-pyridyloxime-nickel-azide system leads to series of clusters with unprecedented topologies. Among them, a remarkable family of {Ni9} metallacycles that are capable of selective encapsulation of azide/halide anions in a cryptand-like cavity through hydrogen-bond interactions has been characterized.

New topologies in pentanuclear nickel/oximato clusters: structural and magnetic characterization.

In the present work, five new Ni5 clusters employing the versatile 2-pyridylcyanoxime ligand have been synthesized and chemically, structurally, and magnetically characterized. The crystallographic examination of these Ni5 clusters together with those already published in the literature, giving a total number of 14 complexes, exhibiting up to 8 different topologies for which the relationship between topology, reaction conditions and magnetic response has been analyzed. DC magnetic measurements were carried in the 300-2 K range for the new complexes and the analysis of the experimental data revealed an antiferromagnetic response for the oximato mediated interactions with a variety of ground states (S = 0, 1, 3) as function of the cluster topology.