Enhancing the Magnetization Blocking Energy of Biradical-Metal System by Merging Discrete Complexes into One-Dimensional Chains.

The reaction of nitronyl nitroxide biradical NITPhMeImbis [5-(2-methylimidazole)-1,3-bis(1-oxyl-3'-oxido-4',4',5',5'-tetramethyl-4,5-hydro-1H-imidazol-2-yl)-benzene] with Ln(hfac)3 ⋅ 2H2 O and Cu(hfac)2 (hfac=hexafluoroacetylacetonate), led to two series of 2p-3d-4f complexes, namely, nona-spin clusters, [Ln2 Cu3 (hfac)12 (NITPhMeImbis)2 ] (Ln=Gd 1, Dy 2), or one-dimensional chains [LnCu2 (hfac)7 (NITPhMeImbis)] (Ln=Y 3, Dy 4, Tb 5) depending on the temperature of the reaction. All five complexes contain a biradical-Ln unit in which the biradical chelates the LnIII ion by the means of one aminoxyl (i. e. NO) group of each NIT unit. For the discrete complexes, a Cu(hfac)2 links two biradical-Ln units via one of the remaining NO groups, while for the chain compounds, the two remaining NO groups of the biradical-Ln moiety are each coordinated to a Cu(hfac)2 unit to form a 1D coordination polymer. Moreover, a terminal Cu(hfac)2 unit is coordinated to the imidazole-N atom of the NITPhMeImbis ligand. Spin dynamics investigations evidenced the onset of slow relaxation of the magnetization for 2, whereas 4 and 5 exhibit a typical single-chain magnet behavior. This highlights the vital role of the 1D spin correlation in the blocking of the magnetization. These results illustrate that from the same basic building blocks, magnetic relaxation can be carefully modulated by structural adjustments.

Evidence of symmetry breaking in a Gd2 di-nuclear molecular polymer.

A chiral 3D coordination compound, [Gd2(L)2(ox)2(H2O)2], arranged around a dinuclear Gd unit has been characterized by X-ray photoemission and X-ray absorption measurements in the context of density functional theory studies. Core level photoemission of the Gd 5p multiplet splittings indicates that spin orbit coupling dominates over j-J coupling evident in the 5p core level spectra of Gd metal. Indications of spin-orbit coupling are consistent with the absence of inversion symmetry due to the ligand field. Density functional theory predicts antiferromagnet alignment of the Gd2 dimers and a band gap of the compound consistent with optical absorption.

Magnetic anisotropy of transition metal and lanthanide ions in pentagonal bipyramidal geometry.

The magnetic anisotropy associated with a pentagonal bipyramidal (PBP) coordination sphere is examined on the basis of experimental and theoretical investigations. The origin and the characteristics of this anisotropy are discussed in relation to the electronic configuration of the metal ions. The effects of crystal field, structural distortion, and a second-coordination sphere on the observed anisotropies for transition meal and lanthanide ions are outlined. For the Ln derivatives, we focus on compounds showing SMM-like behavior (i.e. slow relaxation of their magnetization) in order to highlight the essential chemical and structural parameters for achieving strong axial anisotropy. The use of PBP complexes to impart controlled magnetic anisotropy in polynuclear species such as SMMs or SCMs is also addressed. This review of the magnetic anisotropies associated with a pentagonal bipyramidal coordination sphere for transition metal and lanthanide ions is intended to highlight some general trends that can guide chemists towards designing a compound with specific properties.

Cyclic [Cu-biRadical]2 Secondary Building Unit in 2p-3d and 2p-3d-4f Complexes: Crystal Structure and Magnetic Properties.

Employing the new nitronyl nitroxide biradical ligand biNIT-3Py-5-Ph (2-(5-phenyl-3-pyridyl)-bis(4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide)), a 16-spin Cu-radical complex, [Cu8(biNIT-3Py-5-Ph)4(hfac)16] 1, and three 2p-3d-4f chain complexes, {[Ln(hfac)3][Cu(hfac)2]2(biNIT-3Py-5-Ph)2}n (LnⅢ= Gd 2, Tb 3, Dy 4; hfac = hexafluoroacetylacetonate), have been prepared and characterized. X-ray crystallographic analysis revealed in all derivatives a common cyclic [Cu-biNIT]2 secondary building unit in which two bi-NIT-3Py-5-Ph biradical ligands and two CuII ions are associated via the pyridine N atoms and NO units. For complex 1, two such units assemble with four additional CuII ions to form a discrete complex involving 16 S = 1/2 spin centers. For complexes 2-4, the [Cu-biNIT]2 units are linked by LnIII ions via NO groups in a 1D coordination polymer. Magnetic studies show that the coordination of the aminoxyl groups with Cu or Ln ions results in behaviors combining ferromagnetic and antiferromagnetic interactions. No slow magnetic relaxation behavior was observed for Tb and Dy derivatives.

Modulation of the Sorption Characteristics for an H-bonded porous Architecture by Varying the Chemical Functionalization of the Channel Walls.

Five isostructural microporous supramolecular architectures prepared by H-bonded assembly between the hexa-anionic complex [Zr2 (Ox)7 ]6- (Ox=oxalate, (C2 O4 )2- ) and tripodal cations (H3 -TripCH2 -R)3+ with R=H, CH3 , OH and OBn (Bn=CH2 Ph) are reported. The possibility to obtain the same structure using a mixture of tripodal cations with different R group (R=OH and R=CH3 ) has also been successfully explored, providing a unique example of three-component H-bonded porous framework. The resulting SPA-1(R) materials feature 1D pores decorated by R groups, with apparent pore diameters ranging from 3.0 to 8.5 Å. Influence of R groups on the sorption properties of these materials is evidenced through CO2 and H2 O vapor sorption/desorption experiments, as well as with I2 capture/release experiments in liquid media. This study is one of the first to demonstrate the possibility of tuning the porosity and exerting precise control over the chemical functionalization of the pores in a given H-bonded structure, without modifying the topology of the reference structure, and thus finely adjusting the sorption characteristics of the material.

Blue-Emitting Ligand-Mediated Assembly of Rare-Earth MOFs toward White-Light Emission, Sensing, Magnetic, and Catalytic Studies.

New lanthanide carboxylate compounds with two- (2D) and three-dimensional (3D) structures have been prepared by employing 2,5-bis(prop-2-yn-1-yloxy)terephthalic acid (2,5-BPTA) as an organic linker. The compounds, [Ln(C14H8O6)(C7O3H4)·2H2O]·4(H2O), Ln = Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy and [Ln(C7O3H4)3·(C3H7ON)·(H2O)]·2(H2O)(C3H7NO), Ln = La, Ce, Pr, have two- and three-dimensional structures, respectively. In all compounds, lanthanide ions are connected together, forming a dimer, which is connected by the 2,5-BPTA ligand. In the two-dimensional structure, there are two 2,5-BPTA moieties present, and in the three-dimensional structure, there are three 2,5-BPTA moieties present. The lanthanide centers are nine-coordinated, the 2D structure has a tricapped trigonal prismatic arrangement, and the 3D structure has a monocapped distorted square antiprismatic arrangement. The Pr compound forms in both 2D and 3D structures, whose formation depends on the time of the reaction (2 days─2D and 5-6 days─3D). The ligand emits in the blue region, and using the characteristic emission of Eu3+ (red) and Tb3+ (green) ions, we achieve white light emission in the (Y0.96Tb0.02Eu0.02) compound. The overall quantum yield for the white light emission is 28%. The strong green luminescence of the Tb3+-containing compound was employed to selectively sense the Cr3+ and Fe3+ ions in aqueous solution with limits of detection (LODs) at 0.41 and 8.6 ppm, respectively. The Tb compound was found to be a good heterogeneous catalyst for the Ullman-type O-arylation reaction between phenol and bromoarene with yields of 95%. Magnetic studies on the Gd-, Tb-, and Dy-containing compounds showed weak exchange interactions within the dimeric Ln2 units. The present work demonstrates the many utilities of the rare-earth-containing MOFs, especially toward white-light emission, metal-ion sensing, and heterogeneous catalysis.

Stuffed Tridymite Structures: Synthesis, Structure, Second Harmonic Generation, Optical, and Multiferroic Properties.

The stuffed tridymite structure Ba(Zn/Co)1-x Si1-x M2x O4 (M=Al3+ and Fe3+ ) is explored for the possible multiferroic behavior and to develop new inorganic colored materials. The compounds were synthesized by employing conventional solid-state chemistry methods in the temperature range 1100-1175 °C for 24 h. The powder X-ray diffraction (PXRD) and Rietveld refinement studies indicate that the compounds stabilize in the P63 space group (no. 173). The refinement results were also rationalized by employing Raman spectroscopic studies. The compounds were found to be second harmonic generation (SHG) active and show weak ferroelectric behavior. The co-substitution of Co2+ and Fe3+ in the structure gives rise to a weak ferromagnetic behavior to the compound, BaCo0.75 Si0.75 Fe0.5 O4 , making it a multiferroic material. The optical studies on the prepared compounds exhibited blue color (Co2+ in Td geometry), purple color (Ni2+ in Td geometry), and simultaneous substitution of Co2+ and Fe3+ gives rise to blue-green color owing to metal-to-metal charge transfer (MMCT) effect.

Trinuclear Cyanido-Bridged [Cr2 Fe] Complexes: To Be or not to Be a Single-Molecule Magnet, a Matter of Straightness.

Trinuclear systems of formula [{Cr(LN3O2Ph )(CN)2 }2 M(H2 LN3O2R )] (M=MnII and FeII , LN3O2R stands for pentadentate ligands) were prepared in order to assess the influence of the bending of the apical M-N≡C linkages on the magnetic anisotropy of the FeII derivatives and in turn on their Single-Molecule Magnet (SMM) behaviors. The cyanido-bridged [Cr2 M] derivatives were obtained by assembling trans-dicyanido CrIII complex [Cr(LN3O2Ph )(CN)2 ]- and divalent pentagonal bipyramid complexes [MII (H2 LN3O2R )]2+ with various R substituents (R=NH2 , cyclohexyl, S,S-mandelic) imparting different steric demand to the central moiety of the complexes. A comparative examination of the structural and magnetic properties showed an obvious effect of the deviation from straightness of the M-N≡C alignment on the slow relaxation of the magnetization exhibited by the [Cr2 Fe] complexes. Theoretical calculations have highlighted important effects of the bending of the apical C-N-Fe linkages on both the magnetic anisotropy of the FeII center and the exchange interactions with the CrIII units.

Molybdenum(III) Thiocyanate- and Selenocyanate-Based One-Dimensional Heteronuclear Polymers: Coordination Affinity-Controlled Assemblage of Mixed Spin and Mixed Valence Derivatives with Ni(II) and Co(II/III).

One-dimensional coordination polymers constructed with the 4d metallo-ligand [Mo(NCS)6]3- associated with NiII and CoII complexes are reported. The first series consists of anionic NCS-bridged [Mo-MII]- coordination polymers associated with a discrete paramagnetic complex or a diamagnetic CoIII complex acting as cations. The latter takes advantage of the coordination preference of the S-ligand for the soft 3d ions and has led to hetero-trimetallic [MoIIINiIICoIII] and mixed valence [MoIIICoIICoIII] compounds. A second series concerns neutral chains in which trinuclear [Mo M2II] units are bridged by an additional NCS anion. The soft character of the S atom was also the key to a rare example of a compound involving both high-spin and low-spin CoII centers associated with [Mo(NCS)6]. A [Mo-Ni] derivative obtained with [Mo(NCSe)6]3- has been considered in order to evaluate the effect of Se versus S on the exchange interaction. The spin distribution for selenocyanate metallo-ligand has been assessed by density functional theory calculations. The crystal structures for all compounds have been characterized, and their magnetic behaviors have been investigated. These ferrimagnetic systems are characterized by antiferromagnetic Mo-MII interactions in the range of -40 to -90 cm-1 (based on H = -JSaSb formalism) operative both with CoII and with NiII, thus demonstrating the potential of the MoIII-NCS combination for molecular systems in which exchange interactions play an important role.

Pentagonal Bipyramidal Ln(III) Complexes Containing an Axial Phosphine Oxide Ligand: Field-induced Single-ion Magnetism Behavior of the Dy(III) Analogues.

A series of neutral homologous complexes [(L)Ln(Cy3PO)Cl] {where Ln = Gd (1), Tb (2), Dy (3), and Er (5)} and [(L)Dy(Ph3PO)Cl] (4) [H2L = 2,6-diacetylpyridine bis-benzoylhydrazone] were isolated. In these complexes, the central lanthanide ion possesses a pentagonal bipyramidal geometry with an overall pseudo D5h symmetry. The coordination environment around the lanthanide ion comprises of three nitrogen and two oxygen donors in an equatorial plane. The axial positions are taken up by a phosphine oxide (O donor) and a chloride ion. Among these compounds, the Dy(III) (3 and 4) analogues were found to be field-induced single-ion magnets.

Controlled Growth of Ag Nanocrystals in a H-Bonded Open Framework.

A procedure that enabled rational access to the first example of hybrid material made of NPs grown within a H-bonded framework is reported. To avoid competitive reactions with the framework units, the metal precursor was chemically trapped in the porous structure and subsequently photo-reduced to afford the hybrid material Ag@SPA-2, which consists of Ag NPs of nanometric sizes (<15 nm) homogeneously distributed in the crystals of the host material. In a subsequent step, taking advantage of the porous matrix the silver NPs have been transformed in situ to Ag2 S NP by simple infiltration of H2 S. The supramolecular network is shown to play an important role in stabilizing the inorganic nanomaterials and thus in controlling their growth.

Cyano-Bridged Fe(II)-Cr(III) Single-Chain Magnet Based on Pentagonal Bipyramid Units: On the Added Value of Aligned Axial Anisotropy.

A cyano-bridged Fe(II)-Cr(III) single-chain magnet designed to ensure a parallel orientation of the axial anisotropy of the building units is reported. This ferromagnetic chain compound consists of a pentagonal bipyramid Fe(II) complex with Ising-type anisotropy and a dicyanide Cr(III) complex interlinked through their apical positions. It is characterized by an energy gap for the magnetization reversal of Δeff/ kB = 113 K and exhibits magnetic hysteresis with a coercive field of 1400 Oe at 2 K which positions this compound among the very few examples of SCMs with spin reversal barriers above 100 K. The quite remarkable performances of this single-strand SCM are attributed to the alignment of the local anisotropy axes, which is supported by ab initio modeling. A discrete Cr2Fe complex based on the same building units and behaving as a SMM in zero field is also reported.

Pentagonal-Bipyramid Ln(III) Complexes Exhibiting Single-Ion-Magnet Behavior: A Rational Synthetic Approach for a Rigid Equatorial Plane.

A pentadentate chelating ligand is employed for the facile synthesis of air-stable pentagonal-bipyramid Ln(III) complexes with a rigid equatorial plane. The Dy(III) analogue exhibits single-ion-magnet behavior with Ueff/ kB = 70 K under Hdc = 500 Oe.

Lanthanide-Nitronyl Nitroxide Chains Derived from Multidentate Nitronyl Nitroxides.

Unprecedented lanthanide (Ln)-radical loop-chain coordination polymers were achieved using multidentate pyridyl- or triazole- substituted nitronyl nitroxide ligands. Their magnetic units consist of ferromagnetic [Ln2Radical] moieties, leading for the dysprosium(III) derivatives to slow relaxation of magnetization, which was found to be dependent on the heterocyclic ligands.

Hydrogen-Bonded Open-Framework with Pyridyl-Decorated Channels: Straightforward Preparation and Insight into Its Affinity for Acidic Molecules in Solution.

A hydrogen-bonded open framework with pores decorated by pyridyl groups was constructed by off-charge-stoichiometry assembly of protonated tetrakis(4-pyridyloxymethyl)methane and [Al(oxalate)3 ]3- , which are the H-bond donor and acceptor of ionic H-bond interactions, respectively. This supramolecular porous architecture (SPA-2) has 1 nm-large pores interconnected in 3D with large solvent-accessible void (53 %). It demonstrated remarkable affinity for acidic organic molecules in solution, which was investigated by means of various carboxylic acids including larger drug molecules. Competing sorption between acetic acid and its halogenated homologues evidenced good selectivity of the porous material for the halogenated acids. The gathered results, including a series of guest@SPA-2 crystal structures and HRMAS-NMR spectra, suggest that the efficient sorption exhibited by the material relies not only on an acid-base interaction. The facile release of these guest molecules under neutral conditions makes this SPA a carrier of acidic molecules.

Pentagonal Bipyramid FeII Complexes: Robust Ising-Spin Units towards Heteropolynuclear Nanomagnets.

Pentagonal bipyramid FeII complexes have been investigated to evaluate their potential as Ising-spin building units for the preparation of heteropolynuclear complexes that are likely to behave as single-molecule magnets (SMMs). The considered monometallic complexes were prepared from the association of a divalent metal ion with pentadentate ligands that have a 2,6-diacetylpyridine bis(hydrazone) core (H2 LN3O2R ). Their magnetic anisotropy was established by magnetometry to reveal their zero-field splitting (ZFS) parameter D, which ranged between -4 and -13 cm-1 and was found to be modulated by the apical ligands (ROH versus Cl). The alteration of the D value by N-bound axial CN ligands, upon association with cyanometallates, was also assessed for heptacoordinated FeII as well as for related NiII and CoII derivatives. In all cases, N-coordinated cyanide ligands led to large magnetic anisotropy (i.e., -8 to -18 cm-1 for Fe and Ni, +33 cm-1 for Co). Ab initio calculations were performed on three FeII complexes, which enabled one to rationalize the role of the ligand on the nature and magnitude of the magnetic anisotropy. Starting from the pre-existing heptacoordinated complexes, a series of pentanuclear compounds were obtained by reactions with paramagnetic [W(CN)8 ]3- . Magnetic studies revealed the occurrence of ferromagnetic interactions between the spin carriers in all the heterometallic systems. Field-induced slow magnetic relaxation was observed for mononuclear FeII complexes (Ueff /kB up to 53 K (37 cm-1 ), τ0 =5×10-9  s), and SMM behavior was evidenced for a heteronuclear [Fe3 W2 ] derivative (Ueff /kB =35 K and τ0 =4.6 10-10  s), which confirmed that the parent complexes were robust Ising-type building units. High-field EPR spectroscopic investigation of the ZFS parameters for a Ni derivative is also reported.

Slow Magnetic Relaxation in Ladder-Type and Single-Strand 2p-3d-4f Heterotrispin Chains.

Ladder-type and chain 2p-3d-4f complexes based on a bridging nitronyl nitroxide radical, namely, [LnCu(hfac)5(NIT-Ph-p-OCH2trz)]·0.5C6H14 [Ln = Y (1a), Dy (1b)] and [LnCu(hfac)5(NIT-Ph-p-OCH2trz)] [Ln = Y (2a), Dy (2b); NIT-Ph-p-OCH2trz = 2-[4-[(1H-1,2,4-triazol-1-yl)methoxy]phenyl]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide; hfac = hexafluoroacetylacetonate) have been successfully achieved through a one-pot reaction of the NIT-Ph-p-OCH2trz radical with Cu(hfac)2 and Ln(hfac)3·2H2O. Complexes 1a and 1b feature a ladder-like structure, where the rails are made of Ln(III) and Cu(II) ions alternatively bridged by nitronyl nitroxide and the triazole units while the NIT-Ph-p-OCH2trz moieties act as the rungs of the ladder. Complexes 2a and 2b consist of one-dimensional nitronyl nitroxide bridged Ln coordination polymers with dangly Cu(II) units connected to the triazole moieties. All of compounds exhibit ferromagnetic NIT-Dy and/or NIT-Cu interactions. Both Dy derivatives (1b and 2b) show frequency-dependent out-of-phase magnetic susceptibility signals in a zero field indicating slow magnetic relaxation behavior.

Thermal Magnetic Hysteresis in a Copper-Gadolinium-Radical Chain Compound.

Magnetic bistability spanning over a temperature domain of 40 K can result from a small structural deformation of the gadolinium aminoxyl coordination. This is illustrated for a nitronyl nitroxide 3d-4f chain, [Ln(hfac)3Cu(hfac)2(NIT-Pyrim)2] (Ln(III) = Gd, Dy), which is the first example of a bistable lanthanide-based complex.

Synthesis, Crystal Structures, Magnetic Properties, and Theoretical Investigation of a New Series of NiII-LnIII-WV Heterotrimetallics: Understanding the SMM Behavior of Mixed Polynuclear Complexes.

The polynuclear compounds containing anisotropic metal ions often exhibit efficient barriers for blocking of magnetization at fairly arbitrary geometries. However, at variance with mononuclear complexes, which usually become single-molecule magnets (SMM) under the sole requirement of a highly axial crystal field at the metal ion, the factors influencing the SMM behavior in polynuclear complexes, especially, with weakly axial magnetic ions, still remain largely unrevealed. As an attempt to clarify these conditions, we present here the synthesis, crystal structures, magnetic behavior, and ab initio calculations for a new series of NiII-LnIII-WV trimetallics, [(CN)7W(CN)Ni(H2O)(valpn)Ln(H2O)4]·H2O (Ln = Y 1, Eu 2, Gd 3, Tb 4, Dy 5, Lu 6). The surprising finding is the absence of the magnetic blockage even for compounds involving strongly anisotropic DyIII and TbIII metal ions. This is well explained by ab initio calculations showing relatively large transversal components of the g-tensor in the ground exchange Kramers doublets of 1 and 4 and large intrinsic tunneling gaps in the ground exchange doublets of 3 and 5. In order to get more insight into this behavior, another series of earlier reported compounds with the same trinuclear [WVNiIILnIII] core structure, [(CN)7W(CN)Ni(dmf)(valdmpn)Ln(dmf)4]·H2O (Ln = GdIII 7, TbIII 8a, DyIII 9, HoIII 10), [(CN)7W(CN)Ni(H2O)(valdmpn)Tb(dmf)2.5(H2O)1.5]·H2O·0.5dmf 8b, and [(CN)7W(CN)Ni(H2O)(valdmpn)Er(dmf)3(H2O)1]·H2O·0.5dmf 11, has been also investigated theoretically. In this series, only 8b exhibits SMM behavior which is confirmed by the present ab initio calculations. An important feature for the entire series is the strong ferromagnetic coupling between Ni(II) and W(V), which is due to an almost perfect trigonal dodecahedron geometry of the octacyano wolframate fragment. The reason why only 8b is an SMM is explained by positive zero-field splitting on the nickel site, precluding magnetization blocking in complexes with fewer axial Ln ions. Further analysis has shown that, in the absence of ZFS on Ni ion, all compounds in the two series (except those containing Y and Gd) would be SMMs. The same situation arises for perfectly axial ZFS on Ni(II) with the main anisotropy axis parallel to the main magnetic axis of Ln(III) ions. In all other cases the ZFS on Ni(II) will worsen the SMM properties. The general conclusion is that the design of efficient SMMs on the basis of such complexes should involve isotropic or weekly anisotropic metal ions, such as Mn(II), Fe(III), etc., along with strongly axial lanthanides.

Ising-type Magnetic Anisotropy and Slow Relaxation of the Magnetization in Four-Coordinate Amido-Pyridine FeII Complexes.

A family of four-coordinate FeII complexes formed with N,N'-chelating amido-pyridine ligands was synthesized, and their magnetic properties were investigated. These distorted tetrahedral complexes exhibit significant magnetic anisotropy with zero-field splitting parameter D ranging between -17 and -12 cm-1. Ab initio calculations enabled identification of the structural factors that control the nature of the magnetic anisotropy and the rationalization of the variation of D in these complexes. It is shown that a reduced N-Fe-N angle involving the chelating nitrogen atoms of the ligands is at the origin of the negative D value and that the torsion between the two N-Fe-N planes imposed by steric hindrances further increases the |D| value. Field-induced slow relaxation of magnetization was observed for the three compounds, and a single-molecule magnet behavior with an energy barrier for magnetization flipping (Ueff) of 27 cm-1 could be evidenced for one of them.