Ultra-broadband EPR spectroscopy in field and frequency domains.

Electron paramagnetic resonance (EPR) is a powerful technique to investigate the electronic and magnetic properties of a wide range of materials. We present the first combined terahertz (THz) field and frequency domain electron paramagnetic resonance (HFEPR/FDMR) spectrometer designed to investigate the electronic structure and magnetic properties of molecular systems, thin films and solid state materials in a very broad frequency range of 85-1100 GHz. In this paper, we show high resolution frequency-field (Zeeman) maps (170-380 GHz by 0-15 T) recorded on two single-molecule magnets, [Mn2(saltmen)2(ReO4)2] and [Mn2(salpn)2(H2O)2](ClO4)2, which give direct access to the field-dependence of the energy level diagram. Furthermore, supression of standing waves in the described system and the sensitivity in field and frequency domain operations is evaluated and discussed.

Metallodendritic grafted core-shell γ-Fe2O3 nanoparticles used as recoverable catalysts in Suzuki C-C coupling reactions.

The use of dendritic structures for the grafting of core-shell γ-Fe(2)O(3)/polymer 300 nm superparamagnetic nanoparticles (MNPs) has been performed with four metallodendrons that were functionalized with diphosphinopalladium complexes. The catalytic performance of these nanocatalysts was optimized for the Suzuki C-C cross-coupling reaction. These results demonstrated the importance of optimizing the catalytic efficiency of grafted MNPs by optimizing the dendritic structures and the nature of the peripheral phosphine ligands. All of these nanocatalysts showed remarkable reactivity towards bromoarenes and they were recovered and efficiently reused by magnetic separation with almost no loss of reactivity, even after 25 cycles.

Tri-, tetra-, and hexanuclear copper(II) phosphonates containing N-donor chelating ligands: synthesis, structure, magnetic properties, and nuclease activity.

Reaction of Cu(ClO(4))(2).6H(2)O with cyclopentyl phosphonic acid and 2,2'-bipyridine (bpy) in presence of triethylamine afforded a trinuclear compound [Cu(3)(C(5)H(9)PO(3))(2)(bpy)(3)(MeOH)(H(2)O)](ClO(4))(2) (2). The latter dimerizes to a hexanuclear derivative [Cu(6)(C(5)H(9)PO(3))(4)(bpy)(6)(MeOH)(4)](ClO(4))(4) (1) under prolonged reaction conditions. Reaction of CuCl(2) with cyclopentyl phosphonic acid and 2,2'-bipyridylamine (bpya) affords a tetranuclear derivative [Cu(4)(C(5)H(9)PO(3))(2)(mu-Cl)(2)(bpya)(4)](Cl)(2), (MeOH)(2) (3). Reaction of the latter with NaClO(4) also affords a trinuclear compound [Cu(3)(C(5)H(9)PO(3))(2)(mu-Cl)(bpya)(3)(H(2)O)](ClO(4)) (4). Double and single-bridged hexanuclear species, [{Cu(3)(C(5)H(9)PO(3))(2)(bpy)(3)(bpp)}(MeOH)(2)(H(2)O)(CH(2)Cl(2))(ClO(4))(2)](2) (5), [{Cu(3)(i-PrPO(3))(2)(bpy)(3)(4.4'-bpy)(H(2)O)}(H(2)O)(2)(ClO(4))(2)](2) (6), [{Cu(3)(C(5)H(9)PO(3))(2)(bpya)(3)(4.4'-bpy)(H(2)O)}(MeOH)(H(2)O)(ClO(4))(2)](2) (7), and [Cu(6)(t-BuPO(3))(4)(phen)(6)(4,4'-bpy)(MeOH)(4)](CH(2)Cl(2))(H(2)O)(ClO(4))(4) (8) (phen = 1,10-phenanthroline) were obtained by the reaction of an in situ generated trinuclear complex with appropriate bridging ligands 4,4'-bipyridine (4,4'-bpy) or 1,3-bis(4-pyridyl)propane (bpp). ESI-MS studies of these complexes reveal that 2-4 retain their structures in solution. Molecular structures of 2-8 were determined by X-ray crystallography. All the compounds reveal a capping coordination mode by tridentate phosphonate [RPO(3)](2-) ligands. Detailed magnetic studies on 2 and 4-8 reveal intramolecular antiferromagnetic interactions between Cu(II) S = 1/2 spins. 2 and 4 are excellent artificial nucleases and can convert supercoiled plasmid DNA (pBR322) into its nicked form without the aid of an external oxidant.

"Switching on" the single-molecule magnet properties within a series of dinuclear cobalt(iii)-dysprosium(iii) 2-pyridyloximate complexes.

The use of 2-pyridinealdoxime (paoH), methyl 2-pyridyl ketone oxime (mepaoH), phenyl 2-pyridyl ketone oxime (phpaoH) and pyridine-2-amidoxime (NH2paoH) for the synthesis of dinuclear CoIII/DyIII complexes is described in the absence or presence of an external base. Complexes [CoDy(pao)3(NO3)3] (1), [CoDy(mepao)3(NO3)3] (2), [CoDy(phpao)3(NO3)3] (3) and [CoDy(NH2pao)3(NO3)3]·3MeOH (4·3MeOH) have been isolated and their structures have been determined by single-crystal X-ray crystallography. The complexes crystallize in non-centrosymmetric (2, 3) or centrosymmetric (1, 4·3MeOH) trigonal space groups and form a family of triply-oximate bridged dinuclear Co(iii)-Dy(iii) complexes. The crystals of 1, 3 and 4·3MeOH contain mixtures of Δ and Λ enantiomers, whereas complex 2 is enantiomerically pure (Λ). A 3-fold crystallographic axis (C3) passes through two metal ions in all complexes. The low-spin CoIII and DyIII ions are bridged by three oximate groups belonging to the η1:η1:η1:µ 2-pyridyloximate ligands. The CoIII centre is octahedrally coordinated by the six nitrogen atoms of the deprotonated organic ligands in a facial arrangement. The DyIII centre is bound to an O9 set of donor atoms, its coordination sphere being completed by three bidentate chelating nitrato groups. The coordination polyhedron around DyIII in 1 is best described as the Johnson tricapped trigonal prism, while the coordination geometries of the DyIII centres in 2, 3 and 4·3MeOH are best described as consisting of spherical tricapped trigonal prismatic coordination polyhedra. The spectroscopic data of the complexes are also reported and discussed in the infra-red region in terms of the coordination modes of the ligands involved. The magnetic properties of these complexes were studied between 300 and 1.8 K revealing mainly the depopulation of the DyIIImj sublevels of the ground 6H15/2 state. The intrinsic magnetic anisotropy of the DyIII centers is clearly observed by the non-superimposed magnetization (M) versus H/T data, but single-molecule magnet (SMM) properties were detected only for the mepao--containing complex 2. The origin of these properties in 2 is critically discussed and supported by computational studies.

A One-Pot, High-Yield Synthesis of a Paramagnetic Nickel Square from Divergent Precursors by Anion Template Assembly.

A paramagnetic Ni-containing molecular square has been synthesized in high yield from divergent precursors. An X-ray structure (shown in the picture) reveals the presence of an encapsulated tetrafluoroborate anion, which appears to be a requisite condition for the formation of the cyclic oligomer.

Magnetic blocking in extended metal atom chains: a pentachromium(II) complex behaving as a single-molecule magnet.

Compound [Cr5(tpda)4Cl2] (H2tpda = N(2),N(6)-di(pyridin-2-yl)pyridine-2,6-diamine), an Extended Metal Atom Chain complex featuring two quadruply-bonded {Cr2} units, exhibits field-induced slow relaxation of its magnetization arising from the terminal chromium(II) ion and provides the first example of a chromium(II)-based Single-Molecule Magnet.

Quantum nucleation in a single-chain magnet.

The field sweep rate (upsilon = dH/dt) and temperature (T) dependence of the magnetization reversal of a single-chain magnet is studied at low temperatures. As expected for a thermally activated process, the nucleation field (H(n)) increases with decreasing T and increasing upsilon. The set of H(n)(T,upsilon) data is analyzed with a model of thermally activated nucleation of magnetization reversal. Below 1 K, H(n) becomes temperature independent but remains strongly sweep rate dependent. In this temperature range, the reversal of the magnetization is induced by a quantum nucleation of a domain wall that then propagates due to the applied field.

Metal-metal bonded diruthenium(II, III) assemblies with the polycyano anionic linkers N(CN)2-, C(CN)3-, and 1,4-dicyanamido-2,5-dimethylbenzene (DM-dicyd2-): syntheses, structures, and magnetic properties.

The new metal-metal bonded diruthenium(II,III) compounds [Ru2(O2CCH3)4(mu-L)]infinity (L = N(CN)2-, 1; C(CN)3-, 2) and [[Ru2(O2CCH3)2(mhp)2]2(mu-DM-Dicyd)] (3) (mhp = 2-oxy-6-methylpyridinate, DM-Dicyd = 1,4-dicyanamido-2,5-dimethylbenzene dianion) have been synthesized and fully characterized. Compounds 1 and 2 were synthesized by the reaction of [Ru2(O2CCH3)4(NCCH3)2](BF4) with NaN(CN)2 and KC(CN)3, respectively. The "dimer-of-dimers", 3, was synthesized by a 2:1 reaction of [Ru2(O2CCH3)2(mhp)2(MeOH)](BF4) with [As(Ph)4]2[DM-Dicyd]. Compound 1 crystallizes in the monoclinic space group C2/m with a = 10.174(2) A, b = 13.016(3) A, c = 7.0750(14) A, beta = 101.83(3) degrees, and Z = 2. Compound 2 crystallizes in the orthorhombic space group Fdd2 with a = 29.679(6) A, b = 31.409(6) A, c = 7.3660(15) A, V = 6866(2) A3, and Z = 16. In compound 1, dicyanamide anions (N(CN)2-) bridge the [Ru2(O2CCH3)4]+ units in an end-to-end bridging mode, thereby forming an alternating one-dimensional chain. In compound 2, two cyano groups of tricyanomethanide anion (C(CN)3-) are coordinated to independent [Ru2(O2CCH3)4]+ units to give a chain similar to that found in 1. The Ru-Ru bond distances in 1 and 2 are 2.2788(14) and 2.2756(5) A, respectively, which are typical values for Ru2(O2CR)4Cl and [Ru2(O2CR)4]+ compounds. The Ru-N distances are 2.257(8) A in 1 and 2.259(4) and 2.283(4) A in 2. The temperature dependence of the magnetic susceptibilities of compounds 1-3 reveals a weak antiferromagnetic interaction between Ru2 units (S = 3/2) through each polycyano anionic linker: g = 2.16, zJ = -0.33 cm(-1), D = 63.3 cm(-1) for 1; g = 2.15, zJ = -0.22 cm(-1), D = 58.0 cm(-1) for 2; and g = 2.10, zJ = -0.90 cm(-1), D = 75.0 cm(-1) for 3.

Metal-insulator and structural phase transition observed by ESR spectroscopy and x-ray diffraction in KC60.

We have performed electron spin resonance (ESR) spectroscopy and x-ray diffraction experiments at low temperature on KC60 single crystals. ESR data reveal the occurrence of a metal-insulator phase transition at about 50 K. In the same temperature range, we observe the stabilization of a superstructure which doubles the volume of the unit cell. We suggest that displacements of the K atoms and a modulation of the C60 charge may be involved in the mechanism of this phase transition. These results shed new light on the subtle interplay of structure, dimensionality, and electronic properties in the AC60 fullerides.

Dinuclear and heteropolynuclear complexes containing Mo2(4+) units.

The quadruply bonded compound Mo2(DpyF)4 (1), where DpyF- is the anion of N,N'-di(2-pyridyl)formamidine, has been prepared by ligand substitution reactions of Mo2(OOCCF3)4 and either the neutral ligand, HDpyF, at ambient temperature or its lithium salt, LiDpyF, under refluxing conditions. An X-ray structural analysis shows that 1 has a paddlewheel structure with a [symbol: see text] distance of 2.1108(6) A. Reaction of 1 with CoCl2 in methanol produces the paramagnetic compound [Mo2Co(DpyF)4][CoCl4].2MeOH (2). The Co(II) atom in the cation [Mo2Co(DpyF)4]2+ resides on a low-spin hexacoordinate environment (S = 1/2) with a Co...Mo separation of 2.979(6) A, suggesting there is no direct bonding interaction between the Co and Mo atoms. The Mo-Mo distance of 2.1096(5) A is similar to that in 1. Reaction of 1 and CuCl in methanol yields [Mo2Cu4(DpyF)4Cl2][CuCl2]2.2MeOHxEt2O (3). In the cation there are two copper atoms on each side of the Mo2 core. Each is coordinated to two pyridyl nitrogen atoms of the cis DpyF- ligands and loosely bridged to the other by a chloride ion. As a result, the Cu(I) atoms are not aligned with the Mo2 unit. The Cu to Mo separations are in the range 3.003(1)-3.015(1) A, and the Mo-Mo distance of 2.127(1) A is comparable to those in 1 and 2.

Compounds with symmetrical tricobalt chains wrapped by dipyridylamide ligands and cyanide or isothiocyanate ions as terminal ligands.

Three new linear compounds of the type Co(3)(dpa)(4)X(2), where dpa is the anion of di(2-pyridyl)amine and X is NCS(-) (5), CN(-) (6), and N(CN)(2)(-) (7), have been prepared, and their structures and magnetic behavior have been studied. In all of them, including three different solvates of 5, the Co(3) chains are symmetrical with Co-Co distances of ca. 2.31-2.32 A. The appearance of four lines in the (1)H NMR spectra of the three compounds is also consistent with a symmetrical structure in solution. For all compounds, the magnetic behavior is quite similar with mu(eff) of ca. 1.9-2.0 micro(B) at temperatures between 1.8 and 200 K. As the temperature increases, the effective moments increase gradually, but since saturation is not reached, even at 400 K, the high-spin state cannot be assigned.

Linear trichromium complexes with the anion of 2,6-di(phenylimino)piperidine.

The anion of 2,6-di(phenylimino)piperidine (DPhIP) has been found to support linear chains of three metal atoms. Three new compounds, [Cr3(DPhIP)4Cl]Cl.(1).5CH2Cl2.0.5H2O (1.1.5CH2Cl2.0.5H2O), [Cr3(DPhIP)4(CH3CN)]- (PF6)2.H2O.4CH3CN (2.H2O.4CH3CN), and [Cr3(DPhIP)4(F)(CH3CN)](BF4)2.5CH3CN (3.5CH3CN), have been synthesized and characterized by X-ray crystallography. Compound 1 has a linear chain of three chromium atoms arranged in an unsymmetrical fashion, with two of them forming a quadruply bonded unit (Cr-Cr distance 1.932(2) A) and the third being a non-metal-metal-bound 5-coordinate unit (Cr...Cr distance 2.659(2) A). The fifth coordination site is occupied by a chloride ion, and another chloride ion is located in the interstices of the crystal. The trimetal unit in compound 2 is structurally similar to that in compound 1 except that the axial ligand in 2 is a CH3CN molecule. Compound 3 is an oxidation product prepared by reaction of 1 with AgBF4. Here, a square pyramidal CrIII unit, FCrN4, and a Cr-Cr quadruply bonded (Cr-Cr distance 1.968(2) A) unit, with an axially coordinated acetonitrile molecule, form the trichromium chain. The CrIII...CrII separation of 2.594(2) A in 3 is too long to be considered a bonding interaction.

New linear tricobalt complex of di(2-pyridyl)amide (dpa), [Co3(dpa)4(CH3CN)2][PF6]2.

Reaction of the linear tricobalt compound Co3(dpa)4Cl2 (1) (dpa = di(2-pyridyl)amide) with silver hexafluorophosphate in acetonitrile yields [Co3(dpa)4(CH3CN)2][PF6]2 (2). Two crystalline forms are obtained from the same solution, namely, a monoclinic (P2(1)) form 2xCH3CNx2Et2O and a triclinic (P1) form, 2x3CH3CN. The tricobalt units in both crystals are essentially symmetrical, though this is not required by crystal symmetry, with Co-Co distances in the range 2298-2304 A. Each of the two terminal Co atoms is coordinated to an acetonitrile molecule with Co-N distances in the range 2068-2111 A at 213 K. The spiral arrangement of ligands gives an overall idealized D4 point group symmetry for the cation [Co3(dpa)4(CH3CN)2]2+ . Chiral crystals of both delta and lambda configurations in the P2(1) form have been isolated. The absolute configurations were determined by X-ray crystallography and their mirror-image circular dichroism spectra measured. The D4 symmetry of the cation appears to be preserved in solution as judged by the presence of only five proton resonance signals in the 1H NMR spectrum. Magnetic susceptibility measurements in the solid state indicates that 2 has a doublet ground state and exhibits an increase of the effective moment at high temperature (approximately 160 K) due to a spin crossover process.

Completion of the series of M2(hpp)4Cl2 compounds from W to Pt: the W, Os, and Pt compounds.

The series of M2(hpp)4Cl2 complexes (hpp is the anion of 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine) from M = W to M = Pt has been completed by the preparation and characterization of those with M = W, Os, and Pt. W(hpp)4Cl2 (1) has a W-W distance of 2.250(2) A, is diamagnetic, and can be assigned a W-W triple bond based on a sigma 2 pi 4 electron configuration. Os2(hpp)4Cl2 (2) has an Os-Os distance of 2.379(2) A and displays a temperature-independent paramagnetism. It can be assigned a sigma 2 pi 4 delta 2 delta*2 configuration. Pt2(hpp)4Cl2 has a Pt-Pt distance of 2.440(1) A and is diamagnetic. A bond order of 1, based on a configuration in which only the sigma* orbital is empty, is consistent with these data.

Linear trichromium complexes with direct Cr to Cr contacts. 1. Compounds with Cr3(dipyridylamide)4(2+) cores.

The preparation and structures of seven compounds that contain the Cr3(dpa)4(2+) core (dpa = the anion di(2-pyridyl)amide) are reported. The magnetic properties of several have been measured. In each case there are anionic ligands at each end of the Cr3(6+) chain, sometimes identical (2Cl-, 2CCPh-), sometimes different (Cl-, BF4-; Cl-, PF6-). Several of these compounds have a symmetrical arrangement of the three Cr atoms, with the two Cr-Cr distances equal at ca. 2.36 A, while others have an unsymmetrical arrangement. In the most extreme case the two Cr-Cr distances are 2.00 and 2.64 A. The electronic structures and the remarkable flexibility of the Cr3 arrangement are discussed.

Linear trichromium complexes with direct Cr to Cr contacts. 2. Compounds with Cr3(dipyridylamide)4(3+) cores.

Seven compounds having in common a Cr3(dpa)4(3+) core (dpa = di(2-pyridyl)amide ion) have been prepared and all shown to have an unsymmetrical chain of three Cr atoms. This chain can be described as a pair of quadruply bonded Cr(II) atoms to which a Cr(III) atom is attached. No symmetrical chain has been found, contrary to a previous preliminary report. The seven compounds have been well characterized crystallographically, and their short and long Cr to Cr distances (A, in parentheses) are: 1 [Cr3(dpa)4Cl2]Cl.2CH2Cl2.THF (2.12, 2.47), 2 [Cr3(dpa)4Cl2]AlCl4.CH2Cl2 (2.011, 2.555), 3 [Cr3(dpa)4Cl2]FeCl4.CH2Cl2 (2.009, 2.562), 4 [Cr3(dpa)4Cl2]I3.THF.2H2O (2.08, 2.49), 5 [Cr3(dpa)4Cl2]PF6.2CH2Cl2 (2.08, 2.48), 6 [Cr3(dpa)4(BF4)F]BF4.2CH2Cl2 (1.900, 2.595), 7 [Cr3(dpa)4ClF]BF4.CH2Cl2.C6H14 (2.039, 2.507). Magnetic susceptibility measurements on 1 and 2 reveal mueff = 3.85 +/- 0.05 muB from 10 to 300 K.

Tuning the metal-metal bonds in the linear tricobalt compound Co3(dpa)(4)Cl2: bond-stretch and spin-state isomers.

Sixteen crystal structures have been determined for the Co3(dpa)(4)Cl2 (1) molecule in the following five crystalline solvates: 1.0.85(C2H5)(2)O.0.15CH2Cl2 (at 120, 213, 296 K); 1.C(4)H(8)O (at 120, 295 K); 1.C(6)H(6) (at 170, 213, 260, 316 K); 1.C(6)H(12) (at 120, 213, 295 K); and 1.1.75C(7)H(8).0.5C(6)H(14) (at 90, 110, 170, 298 K). For 1.0.85(C(2)H(5))(2)O.0.15CH2Cl2 the molecule of 1 is almost symmetrical at 120 K (Co-Co distances of 2.3191(3) and 2.3304(3) A) and remains so at 296 K (2.2320(3) and 2.3667(4) A). For 1.C(4)H(8)O the Co(3) chain is precisely symmetric at both 120 and 295 K though the Co-Co distances increase from 2.3111(4) to 2.3484(4) A as the temperature rises. Compound 1.C(6)H(6) is isomorphous with 1.C(4)H(8)O at 213 and 295 K and has rigorously symmetrical molecules at these two temperatures. Between 213 and 120 K the space group changes from Pccn to P2(1)/c, so that a symmetrical arrangement is no longer required and the two Co-Co distances then differ slightly (by 0.013 A). For 1.C(6)H(6) there is a phase change between 316 K (Pca2(1)) and 260 K (Pna2(1)). At all four temperatures, however, the molecule is almost symmetrical, with the two independent Co-Co distances never differing by more than 0.026 A. 1.1.75C(7)H(8).0.5C(6)H(14) contains, at all temperatures between 90 and 298 K, two crystallographically independent molecules, each of which is distinctly unsymmetrical at 298 K (Co-Co distances of 2.312(2) and 2.442(2) A for one and 2.310(2) and 2.471(2) for the other). In the first of these the distances converge to a much smaller separation (0.056 A) at 90 K while in the second the difference decreases to only 0.006 A at 90 K. Magnetic susceptibility measurements from 1.8 to 350 K indicate in each case that a gradual spin crossover, from a doublet to a quartet state, occurs over this temperature range.