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G Christou

Publications and source records attributed to G Christou.

At least 19 recordsLinked to original sources
PubMed2006

Resonant tunneling in truly axial symmetry Mn12 single-molecule magnets: sharp crossover between thermally assisted and pure quantum tunneling.

Magnetization measurements of a truly axial symmetry molecular nanomagnet with a spin ground state of S = 10 show resonant tunneling. This compound has the same magnetic anisotropy as but the molecules are better isolated and the crystals have less disorder and a higher symmetry. Hysteresis loop measurements at several temperatures reveal a well-resolved step fine structure which is due to level crossings of excited states. All step positions can be modeled by a simple spin Hamiltonian. The results establish a sharp crossover between thermally assisted and pure quantum tunneling, as had been previously predicted.

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PubMed2005

Propagation of avalanches in Mn12-acetate: magnetic deflagration.

Local time-resolved measurements of fast reversal of the magnetization of single crystals of Mn12-acetate indicate that the magnetization avalanche spreads as a narrow interface that propagates through the crystal at a constant velocity that is roughly 2 orders of magnitude smaller than the speed of sound. We argue that this phenomenon is closely analogous to the propagation of a flame front (deflagration) through a flammable chemical substance.

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PubMed2005

Quantum phase interference and spin-parity in Mn12 single-molecule magnets.

Magnetization measurements of Mn12 molecular nanomagnets with spin ground states of S=10 and S=19/2 show resonance tunneling at avoided energy level crossings. The observed oscillations of the tunnel probability as a function of the magnetic field applied along the hard anisotropy axis are due to topological quantum phase interference of two tunnel paths of opposite windings. Spin-parity dependent tunneling is established by comparing the quantum phase interference of integer and half-integer spin systems.

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PubMed2005

Single-molecule magnets: structure and properties of [Mn18O14(O2CMe)18(hep)4(hepH)2(H2O)2](ClO4)2 with spin S = 13.

The reaction of 2-(hydroxyethyl)pyridine (hepH) with a 2:1 molar mixture of [Mn3O(O2CMe)6(py)3]ClO4 and [Mn3O(O2CMe)6(py)3] in MeCN afforded the new mixed-valent (16Mn(III), 2Mn(II)), octadecanuclear complex [Mn18O14(O2CMe)18(hep)4(hepH)2(H2O)2](ClO4)2 (1) in 20% yield. Complex 1 crystallizes in the triclinic space group P. Direct current magnetic susceptibility studies in a 1.0 T field in the 5.0-300 K range, and variable-temperature variable-field dc magnetization studies in the 2.0-4.0 K and 2.0-5.0 T ranges were obtained on polycrystalline samples. Fitting of magnetization data established that complex 1 possesses a ground-state spin of S = 13 and D = -0.18 K. This was confirmed by the value of the in-phase ac magnetic susceptibility signal. Below 3 K, the complex exhibits a frequency-dependent drop in the in-phase signal, and a concomitant increase in the out-of-phase signal, consistent with slow magnetization relaxation on the ac time scale. This suggests the complex is a single-molecule magnet (SMM), and this was confirmed by hysteresis loops below 1 K in magnetization versus dc field sweeps on a single crystal. Alternating current and direct current magnetization data were combined to yield an Arrhenius plot from which was obtained the effective barrier (U(eff)) for magnetization reversal of 21.3 K. Below 0.2 K, the relaxation becomes temperature-independent, consistent with relaxation only by quantum tunneling of the magnetization (QTM) through the anisotropy barrier via the lowest-energy MS = +/-13 levels of the S = 13 spin manifold. Complex 1 is thus the SMM with the largest ground-state spin to display QTM.

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PubMed2004

Magnetic long-range order induced by quantum relaxation in single-molecule magnets.

Can magnetic interactions between single-molecule magnets (SMMs) in a crystal establish long-range magnetic order at low temperatures deep in the quantum regime, where the only electron spin fluctuations are due to incoherent magnetic quantum tunneling (MQT)? Put inversely: can MQT provide the temperature dependent fluctuations needed to destroy the ordered state above some finite T(c), although it should basically itself be a T-independent process? Our experiments on two novel Mn4 SMMs provide a positive answer to the above, showing at the same time that MQT in the SMMs has to involve spin-lattice coupling at a relaxation rate equaling that predicted and observed recently for nuclear-spin-mediated quantum relaxation.

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PubMed2003

Spin quantum tunneling via entangled states in a dimer of exchange-coupled single-molecule magnets.

A new family of supramolecular, antiferromagnetically exchange-coupled dimers of single-molecule magnets (SMMs) has recently been reported. Each SMM acts as a bias on its neighbor, shifting the quantum tunneling resonances of the individual SMMs. Hysteresis loop measurements on a single crystal of SMM dimers have now established quantum tunneling of the magnetization via entangled states of the dimer. This shows that the dimer really does behave as a quantum mechanically coupled dimer, and also allows the measurement of the longitudinal and transverse superexchange coupling constants.

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PubMed2003

Quantum coherence in an exchange-coupled dimer of single-molecule magnets.

A multi- high-frequency electron paramagnetic resonance method is used to probe the magnetic excitations of a dimer of single-molecule magnets. The measured spectra display well-resolved quantum transitions involving coherent superposition states of both molecules. The behavior may be understood in terms of an isotropic superexchange coupling between pairs of single-molecule magnets, in analogy with several recently proposed quantum devices based on artificially fabricated quantum dots or clusters. These findings highlight the potential utility of supramolecular chemistry in the design of future quantum devices based on molecular nanomagnets.

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PubMed2003

Symmetry of magnetic quantum tunneling in single molecule magnet Mn12-acetate.

The symmetry of magnetic quantum tunneling has been studied in the prototype single molecule magnet Mn12-acetate using a micro-Hall effect magnetometer and superconducting high field vector magnet system. An average crystal fourfold symmetry is shown to be due to local molecular environments of twofold symmetry that are rotated by 90 degrees with respect to one another, confirming that disorder which lowers the molecule symmetry is as important to magnetic quantum tunneling. We have studied a subset of these lower (twofold) site symmetry molecules and present evidence for a Berry phase effect consistent with a local twofold symmetry.

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PubMed2003

Long-range ferromagnetic dipolar ordering of high-spin molecular clusters.

We report the first example of a transition to long-range magnetic order in a purely dipolarly interacting molecular magnet. For the magnetic cluster compound Mn6O4Br4(Et2dbm)6, the anisotropy experienced by the total spin S = 12 of each cluster is so small that spin-lattice relaxation remains fast down to the lowest temperatures, thus enabling dipolar order to occur within experimental times at T(c) = 0.16 K. In high magnetic fields, the relaxation rate becomes drastically reduced and the interplay between nuclear- and electron-spin lattice relaxation is revealed.

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PubMed2003

Phenolic removal in a model olive oil mill wastewater using Pleurotus ostreatus in bioreactor cultures and biological evaluation of the process.

Pleurotus ostreatus grown in bioreactor batch cultures in a model phenolic wastewater (diluted and sterilized olive oil mill wastewater-OMW), caused significant phenolic removal. Laccase, the sole ligninolytic enzyme detected in the growth environment, was produced during primary metabolic growth. The bioprocess was simulated with the aid of a mathematical model and the parameters of growth were determined. When the fungal biomass was increased in the reactor (during repeated batch experiments) the rate of reducing sugars consumption progressively increased, but a phenolic fraction seemed of being strongly resistant to oxidation. The toxicity of OMW against the seeds of Lepidium sativum and the marine Branchiopoda Artemia sp. was significantly decreased after biotreatment. On the contrary, the toxicity against the freshwater Branchiopoda Daphnia magna was not affected by the treatment, whereas on the soil and freshwater sediments Ostracoda Heterocypris incongruens was slightly decreased. Both treated and untreated OMWs, used as water for irrigation of lettuce and tomato plants, did not significantly affect the uptake of several nutrients by the cultivated plants, but resulted in a decrease in the plant yields, which was minimized when high OMW dilutions were used. As a conclusion, P. ostreatus is able to reduce phenolic content and toxicity of sterilized OMW, in bioreactor cultures. However, high OMW dilutions should be used, and/or additional treatment should be applied before use of the OMW in the environment, e.g. as water for irrigation. Further research should be done in order to transfer this technology under industrial conditions (e.g. by using unsterilized OMW).

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PubMed2002

Spin-spin cross relaxation in single-molecule magnets.

The one-body tunnel picture of single-molecule magnets (SMMs) is not always sufficient to explain the measured tunnel transitions. An improvement to the picture is proposed by including also two-body tunnel transitions such as spin-spin cross relaxation (SSCR) which are mediated by dipolar and weak superexchange interactions between molecules. A Mn4 SMM is used as a model system. At certain external fields, SSCRs lead to additional quantum resonances which show up in hysteresis loop measurements as well-defined steps. A simple model is used to explain quantitatively all observed transitions.

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PubMed2001

Magnetic-field-dependent heat capacity of the single-molecule magnet [Mn(12)O(12)(O(2)CEt)(16)(H(2)O)(3)].

Accurate heat capacities of the single-molecule magnet [Mn(12)O(12)(O(2)CEt)(16)(H(2)O)(3)] were measured from 0.3 to 311 K by adiabatic calorimetry without an external magnetic field. Heat-capacity anomalies were separated by assuming several contributions including lattice vibration, magnetic anisotropy, and hyperfine splitting. Among them, a tiny thermal anomaly between 1 and 2 K is attributable to the presence of Jahn-Teller isomers. The heat capacities of the polycrystalline sample were also measured with applied magnetic fields from 0 to 9 T in the 2-20 K temperature region by the relaxation method. With an applied magnetic field of up to 2 T, a steplike heat-capacity anomaly was observed around the blocking temperature T(B) approximately 3.5 K. The magnitude of the anomaly reached a maximum at 0.7 T. With a further increase in the magnetic field, the step was decreasing, and finally it disappeared above 3 T. The step at T(B) under 0.7 T can be roughly accounted for by assuming that a conversion between the up-spin and down-spin states is allowed above T(B) by phonon-assisted quantum tunneling, while it is less effective below T(B). Excess heat capacity under a magnetic field revealed a large heat-capacity hump around 14 K and 2 T, which would be attributed to a thermal excitation from the S = 9 ground state to the spin manifold with different S values, where S is the total spin quantum number.

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PubMed2001

Effects of paramagnetic ferrocenium cations on the magnetic properties of the anionic single-molecule magnet [Mn(12)O(12)(O(2)CC(6)F(5))(16)(H(2)O)(4)]-.

The preparation and physical characterization are reported for the single-molecule magnet salts [M(Cp')(2)](n)()[Mn(12)O(12)(O(2)CC(6)F(5))(16)(H(2)O)(4)] (M = Fe, n = 1, Cp' = C(5)Me(5) (2a), C(5)H(5) (2b); M = Co, n = 1, Cp' = C(5)Me(5) (2c), C(5)H(5) (2d); M = Fe, n = 2, Cp' = C(5)Me(5) (2e), C(5)H(5) (2f)) to investigate the effects of paramagnetic cations on the magnetization relaxation behavior of [Mn(12)]- anionic single-molecule magnets. Complex 2a.2H(2)O crystallizes in the orthorhombic space group Aba2, with cell dimensions at 173 K of a = 25.6292(2) A, b = 25.4201(3) A, c = 29.1915(2) A, and Z = 4. Complex 2c.2CH(2)Cl(2).C(6)H(14) crystallizes in the monoclinic space group P2(1)/c, with cell dimensions at 173 K of a = 17.8332(6) A, b = 26.2661(9) A, c = 36.0781(11) A, beta = 92.8907(3) degrees, and Z = 4. These two salts consist of either paramagnetic [Fe(C(5)Me(5))(2)]+ cations or diamagnetic [Co(C(5)Me(5))(2)]+ cations, and [Mn(12)O(12)(O(2)CC(6)F(5))(16)(H(2)O)(4)]- anions. The structures of the anions in the two salts are similar, consisting of a central Mn(4)O(4) cubane moiety, surrounded by a nonplanar ring of eight Mn atoms that are bridged by and connected to the cube via mu(3)-O(2)- ions. The oxidation states of four Mn sites out of eight outer Mn ions in complex 2a were assigned to be +2.75 from the valence bond sum analysis although the disordering of bridging carboxylates prevents more precise determination. On the other hand in complex 2c, one Mn site out of eight outer Mn ions was identified as a Mn(II) ion, accommodating the "extra" electron; this was deduced by a valence bond sum analysis. Thus, the anion in complex 2c has a Mn(II)(1)Mn(III)(7)Mn(IV)(4) oxidation state description. The Jahn-Teller axes of the Mn(III) ions in both anions are roughly aligned in one direction. All complexes studied exhibit a single out-of-phase ac magnetic susceptibility (chi"(M)) signal in the 4.6-4.8 K range for complexes 2a-2d and in the 2.8-2.9 K range for complexes 2e and 2f at 1 kHz ac frequency. The temperature of the chi"(M) peaks is frequency dependent, as expected for single-molecule magnets. From Arrhenius plots of the frequency dependence of the temperature of the chi"(M) maxima, the effective energy barriers U(eff) for changing spin from "up" to spin "down" were estimated to be 50-54 K for complexes 2a-2d and 27-28 K for complexes 2e and 2f. The least-squares fits of the reduced magnetization data indicate that both complexes 2a and 2d have ground states of S = (21)/(2). High-frequency EPR spectra were recorded for complex 2a at frequencies of 217, 327, and 434 GHz in the 4.5-30 K range. The observed transition fields were least-squares fit to give g = 1.91, D = -0.35 cm(-1), and B(4)(0) = -3.6 x 10(-7) cm(-1) for the S = (21)/(2) ground state. The effective energy barrier U(eff) is slightly lower than U estimated from D, which is consistent with the thermally assisted tunneling model. Magnetization hysteresis loops were observed for complexes 2a and 2c. Although 2a was oriented in a different manner as expected by strong magnetic field, both complexes show clear hysteresis loops with some steps on them, indicating that the effect of the magnetic cation on the magnetization relaxation of the anionic [Mn(12)]- complex is rather small. An 11% (57)Fe enriched complex 2b was studied by means of Mössbauer spectroscopy down to as low as 1.7 K. Slow paramagnetic relaxation broadening and magnetic hyperfine splitting were evident in the low-temperature spectra, indicating that the iron atoms feel a growing magnetic field owing to slow magnetization reversal in the [Mn(12)]- anions.

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PubMed2001

Distribution of tunnel splittings in Mn(12) acetate.

In magnetic fields applied parallel to the anisotropy axis, the relaxation of the magnetization of Mn(12)-acetate measured for different sweep rates collapses onto a single scaled curve. The form of the scaling implies that the dominant symmetry-breaking process responsible for tunneling is a locally varying second-order transverse anisotropy, forbidden by tetragonal symmetry in the perfect crystal, which gives rise to a broad distribution of tunnel splittings in a real crystal of Mn(12) acetate. Different forms applied to even- and odd-numbered steps provide a clear distinction between even resonances (associated with crystal anisotropy) and odd resonances (which require a transverse magnetic field).

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PubMed2001

Single-molecule magnets: preparation and properties of mixed-carboxylate complexes.

Methods are reported for the preparation of mixed-carboxylate versions of the [Mn(12)O(12)(O(2)CR)(16)(H(2)O)(4)] family of single-molecule magnets (SMMs). [Mn(12)O(12)(O(2)CCHCl(2))(8)(O(2)CCH(2)Bu(t))(8)(H(2)O)(3)] (5) and [Mn(12)O(12)(O(2)CHCl(2))(8)(O(2)CEt)(8)(H(2)O)(3)] (6) have been obtained from the 1:1 reaction of the corresponding homocarboxylate species. Complex 5.CH(2)Cl(2).H(2)O crystallizes in the triclinic space group P1 with, at -165 degrees C, a = 15.762(1), b = 16.246(1), c = 23.822(1) A, alpha = 103.92(1), beta = 104.50(1), gamma = 94.23(1) degrees, Z = 2, and V = 5674(2) A(3). Complex 6.CH(2)Cl(2) crystallizes in the triclinic space group P1 with, at -158 degrees C, a = 13.4635(3), b = 13.5162(3), c = 23.2609(5) A, alpha = 84.9796(6), beta = 89.0063(8), gamma = 86.2375(6) degrees, Z = 2, and V = 4207.3(3) A(3). Complexes 5 and 6 both contain a [Mn(12)O(12)] core with the CHCl(2)CO(2-) ligands ordered in the axial positions and the RCO(2-) ligands (R = CH(2)Bu(t) (5) or Et (6)) in equatorial positions. There is, thus, a preference for the CHCl(2)CO(2-) to occupy the sites lying on the Mn(III) Jahn-Teller axes, and this is rationalized on the basis of the relative basicities of the carboxylate groups. Direct current magnetic susceptibility studies in a 10.0 kG field in the 2.00-300 K range indicate a large ground-state spin, and fitting of magnetization data collected in the 10.0-70.0 kG field and 1.80-4.00 K temperature range gave S = 10, g = 1.89, and D = -0.65 K for 5, and S = 10, g = 1.83, and D = -0.60 K for 6. These values are typical of [Mn(12)O(12)(O(2)CR)(16)(H(2)O)(4)] complexes. Alternating current susceptibility studies show the out-of-phase susceptibility (chi(M)' ') signals characteristic of the slow relaxation in the millisecond time scale of single-molecule magnets. Arrhenius plots obtained from chi(M)' ' versus T data gave effective barriers to relaxation (U(eff)) of 71 and 72 K for 5 and 6, respectively. (1)H NMR spectra in CD(2)Cl(2) show that 5 and 6 are the main species present on dissolution, but there is evidence for some ligand distribution between axial and equatorial sites, by intra- and/or intermolecular exchange processes.

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PubMed2001

Mixed-valence tetranuclear manganese single-molecule magnets.

The preparations, X-ray structures, and detailed physical characterizations are presented for two new mixed-valence tetranuclear manganese complexes that function as single-molecule magnets (SMM's): [Mn4(hmp)6Br2(H2O)2]Br2-4H2O (2) and [Mn4(6-me-hmp)6Cl4]-4H2O (3), where hmp(-) is the anion of 2-hydroxymethylpyridine and 6-me-hmp(-) is the anion of 6-methyl-2-hydroxymethylpyridine. Complex 2-4H2O crystallizes in the space group P2(1)/c, with cell dimensions at -160 degrees C of a = 10.907(0) A, b = 15.788(0) A, c = 13.941(0) A, beta = 101.21(0) degrees, and Z = 2. The cation lies on an inversion center and consists of a planar Mn4 rhombus that is mixed-valence, Mn2(III)Mn2(II). The hmp(-) ligands function as bidentate ligands and as the only bridging ligands in 2-4H2O. Complex 3-4H2O crystallizes in the monoclinic space group C2/c, with cell dimensions at -160 degrees C of a = 17.0852(4) A, b = 20.8781(5) A, c = 14.835(3) A, beta = 90.5485(8) degrees, and Z = 4. This neutral complex also has a mixed-valence Mn2(III)Mn2(II) composition and is best described as having four manganese ions arranged in a bent chain. A mu2-oxygen atom of the 6-me-hmp(-) anion bridges between the manganese ions; the Cl(-) ligands are terminal. Variable-field magnetization and high-frequency and -field EPR (HFEPR) data indicate that complex 2-4H2O has a S = 9 ground state whereas complex 3.4H(2)O has S = 0 ground state. Fine structure patterns are seen in the HFEPR spectra, and in the case of 2.4H(2)O it was possible to simulate the fine structure assuming S = 9 with the parameters g = 1.999, axial zero-field splitting of D/k(B) = -0.498 K, quartic longitudinal zero-field splitting of B4(omicron)/k(B) = 1.72 x 10(-5) K, and rhombic zero-field splitting of E/k(B) = 0.124 K. Complex 2-4H2O exhibits a frequency-dependent out-of-phase AC magnetic susceptibility signal, clearly indicating that this complex functions as a SMM. The AC susceptibility data for complex 2-4H2O were measured in the 0.05-4.0 K range and when fit to the Arrhenius law, gave an activation energy of DeltaE = 15.8 K for the reversal of magnetization. This DeltaE value is to be compared to the potential-energy barrier height of U/k(B) = absolute value DSz(2) = 40.3 K calculated for 2-4H2O.

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PubMed2001

Single-molecule magnets: site-specific ligand abstraction from [Mn12O12(O2CR)16(H2O)4] and the preparation and properties of [Mn12O12(NO3)4(O2CCH2Bu(t))12(H2O)4].

Site-selective carboxylate abstraction has been achieved from [Mn(12)O(12)(O(2)CR)(16)(H(2)O)(4)] complexes by treatment with HNO(3) in MeCN. The reaction of the R = Ph or CH(2)Bu(t)() complexes with 4 equiv of HNO(3) gives [Mn(12)O(12)(NO(3))(4)(O(2)CR)(12)(H(2)O)(4)] (R = CH(2)Bu(t) (6) or Ph (7)) in analytical purity. Complex 6.MeNO(2) crystallizes in monoclinic space group C2/c with the following cell parameters at -168 degrees C: a = 21.280(5), b = 34.430(8), c = 33.023(8) A, beta = 104.61(1) degrees, V = 23413 A, and Z = 8. The four NO(3)(-) groups are not disordered and are bound in bridging modes at axial positions formerly occupied by bridging carboxylate groups. (1)H NMR spectroscopy in CD(2)Cl(2) and CDCl(3) shows retention of the solid-state structure on dissolution in these solvents. DC magnetic susceptibility (chi(M)) and magnetization (M) studies have been carried out in the 2.00-300 K and 1.0-7.0 T ranges. Fits of M/Nmu(B) versus H/T plots gave S = 10, g = 1.92, and D = -0.40 cm(-1), where D is the axial zero-field splitting parameter. AC magnetic susceptibility studies on 6 have been performed in the 1.70-10.0 K range in a 3.5 Oe field oscillating at frequencies up to 1500 Hz. Out-of-phase magnetic susceptibility (chi(M)' ') signals were observed in the 4.00-8.00 K range which were frequency-dependent. Thus, 6 displays the slow magnetization relaxation diagnostic of a single-molecule magnet (SMM). The data were fit to the Arrhenius law, and this gave the effective barrier to relaxation (U(eff)) of 50.0 cm(-1) (72.0 K) and a pre-exponential (1/tau(0)) of 1.9 x 10(8) s(-1). Complex 6 also shows hysteresis in magnetization versus DC field scans, and the hysteresis loops show steps at regular intervals of magnetic field, the diagnostic evidence of field-tuned quantum tunneling of magnetization. High-frequency EPR (HFEPR) spectroscopy on oriented crystals of complex 6 shows resonances assigned to transitions between zero-field split M(s) states of the S = 10 ground state. Fitting of the data gave S = 10, g = 1.99, D = -0.46 cm(-1), and B(4)(0) = -2.0 x 10(-5), where B(4)(0) is the quartic zero-field coefficient. The combined results demonstrate that replacement of four carboxylate groups with NO(3)(-) groups leads to insignificant perturbation of the magnetic properties of the Mn(12) complex. Complex 6 should now be a useful starting point for further reactivity studies, taking advantage of the good leaving group properties of the NO(3)(-) ligands.

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