Structural, electronic, and magnetic entropy contributions of the orbital order-disorder transition in LaMnO(3)

Measurements of X-ray diffraction, electrical resistivity, and magnetization are reported across the Jahn-Teller phase transition in LaMnO(3). Using a thermodynamic equation, we obtained the pressure derivative of the critical temperature (T(JT)), dT(JT)/dP = -28.3 K GPa(-1). This approach also reveals that 5.7(3)J(mol K)(-1) comes from the volume change and 0.8(2)J(mol K)(-1) from the magnetic exchange interaction change across the phase transition. Around T(JT), a robust increase in the electrical conductivity takes place and the electronic entropy change, which is assumed to be negligible for the majority of electronic systems, was found to be 1.8(3)J(mol K)(-1).

Magnetic properties of spinel-type oxides NiMn2-xMexO4

New materials, based on the well-known spinel compound NiMn 2O4, have been synthesized and characterized from the magnetic point of view. The manganese cation was partially substituted in the general formula NiMn2-xMexO4, by nonmagnetic and magnetic elements, such as Me = Ga, Zn, Ni and Cr (0 × 1). Prior to the determination of their magnetic properties, the non-substituted spinel NiMn2O4 was carefully characterized and studied as a function of the oxygen stoichiometry, based on the influence of the annealing atmosphere and quenching rate. The ferrimagnetic character was observed in all samples, with a paramagnetic-to-ferromagnetic transition temperature T c stabilized at 110 K, and well defined long-range antiferromagnetic interactions at lower temperatures, which depend on the applied field and the substitute concentration. © 2006 Sociedad Chilena de Química.

New magnetic frameworks of [(CuF 2 (H 2 O) 2 ) x (pyz)]

Pressure-driven orbital reordering in the quantum magnet [CuF2(H2O)2- (pyz)], (pyz = pyrazine), dramatically affects its magnetic exchange interactions. The crystal chemistry of this system is enriched with a new phase above 3 GPa, surprisingly concomitant with other polymorphs. Moreover, we discovered an unprecedented compound with a different stoichiometry, [(CuF2(H2O)2)2(pyz)], featuring magnetic bi-layers.

The synthesis, characterization, X-ray structure and magnetism of dinuclear-based bis[μ-(1,1,3,3-tetracyano-2-ethoxypropenido-κ2N,N′) (1,1,3,3-tetracyano-2-ethoxypropenido-κN)(2,2′-bipyridine)copper(II)] organized in alternating chains via semi-coordinating Cu–N distances

The monoanionic ligand 1,1,3,3 tetracyano-2 ethoxypropenide (tcnoet) is reported with its Cu(II)–bpy complex of formula [Cu2(µ-tcnoet)2(tcnoet)2(bpy)2]. The structure has been determined using X-ray diffraction and features an alternating chain with bridging tcnoet ligands. One ligand acts as a bidentate, dinucleating ligand with one short Cu–N and one medium Cu–N bond, whereas the other tcnoet is largely monodentate, albeit with a very weak interdimer Cu–N bond. Despite the arrangement in dinuclear units, further arranged into linear chains through the non-bridging tcnoet ligand, the compound shows no significant magnetic exchange, as deduced from magnetic susceptibility down to 4 K. Ligand-field, IR and EPR spectra in the solid state and in frozen solution are reported and are consistent with the overall structure.

Enhanced Ion Anisotropy by Nonconventional Coordination Geometry: Single-Chain Magnet Behavior for a [{(FeL)-L-II}(2){Nb-IV(CN)(8)}] Helical Chain Compound Designed with Heptacoordinate Fe-II

Nonconventional heptacoordination in combination with efficient magnetic exchange coupling is shown to yield a 1-D heteronuclear {(FeNbIV)-Nb-II} compound with remarkable magnetic features when compared to other Fe(II)-based single chain magnets (SCM). Cyano-bridged heterometallic {3d-4d} and {3d-5d} chains are formed upon assembling Fe(II) bearing a pentadentate macrocycle as the blocking ligand with octacyano metallates, [M(CN)(8)](4-) (M = Nb-IV, Mo-IV, W-IV.) X-ray diffraction (single-crystal and powder) measurements reveal that the [{(H2O)Fe(L-1)}{M(CN)(8)}{Fe(L-1)}](infinity) architectures consist of isomorphous 1-D polymeric structures based on the alternation of {Fe(L-1)}(2+) and {M(CN)(8)}(4-) units (L-1 stands for the pentadentate macrocycle). Analysis of the magnetic susceptibility behavior revealed cyano-bridged {Fe-Nb} exchange interaction to be antiferromagnetic with J = -20 cm(-1) deduced from fitting an Ising model taking into account the noncollinear spin arrangement. For this ferrimagnetic chain a slow relaxation of its magnetization is observed at low temperature revealing a SCM behavior with Delta/k(B) = 74 K and tau(0) = 4.6 x 10(-11) s. The M versus H behavior exhibits a hysteresis loop with a coercive field of 4 kOe at 1 K and reveals at 380 mK magnetic avalanche processes, i.e., abrupt reversals in magnetization as H is varied. The origin of these characteristics is attributed to the combination of efficient {Fe-Nb} exchange interaction and significant anisotropy of the {Fe(L-1)) unit. High field EPR and magnetization experiments have revealed for the parent compound [Fe(L-1)(H2O)(2)]Cl-2 a negative zero field splitting parameter of D approximate to -17 cm(-1). The crystal structure, magnetic behavior, and Mossbauer data for [Fe(L-1)(H2O)(2)]Cl-2 are also reported.

Enhanced Ion Anisotropy by Nonconventional Coordination Geometry: Single-Chain Magnet Behavior for a [{(FeL)-L-II}(2){Nb-IV(CN)(8)}] Helical Chain Compound Designed with Heptacoordinate Fe-II

Nonconventional heptacoordination in combination with efficient magnetic exchange coupling is shown to yield a 1-D heteronuclear {(FeNbIV)-Nb-II} compound with remarkable magnetic features when compared to other Fe(II)-based single chain magnets (SCM). Cyano-bridged heterometallic {3d-4d} and {3d-5d} chains are formed upon assembling Fe(II) bearing a pentadentate macrocycle as the blocking ligand with octacyano metallates, [M(CN)(8)](4-) (M = Nb-IV, Mo-IV, W-IV.) X-ray diffraction (single-crystal and powder) measurements reveal that the [{(H2O)Fe(L-1)}{M(CN)(8)}{Fe(L-1)}](infinity) architectures consist of isomorphous 1-D polymeric structures based on the alternation of {Fe(L-1)}(2+) and {M(CN)(8)}(4-) units (L-1 stands for the pentadentate macrocycle). Analysis of the magnetic susceptibility behavior revealed cyano-bridged {Fe-Nb} exchange interaction to be antiferromagnetic with J = -20 cm(-1) deduced from fitting an Ising model taking into account the noncollinear spin arrangement. For this ferrimagnetic chain a slow relaxation of its magnetization is observed at low temperature revealing a SCM behavior with Delta/k(B) = 74 K and tau(0) = 4.6 x 10(-11) s. The M versus H behavior exhibits a hysteresis loop with a coercive field of 4 kOe at 1 K and reveals at 380 mK magnetic avalanche processes, i.e., abrupt reversals in magnetization as H is varied. The origin of these characteristics is attributed to the combination of efficient {Fe-Nb} exchange interaction and significant anisotropy of the {Fe(L-1)) unit. High field EPR and magnetization experiments have revealed for the parent compound [Fe(L-1)(H2O)(2)]Cl-2 a negative zero field splitting parameter of D approximate to -17 cm(-1). The crystal structure, magnetic behavior, and Mossbauer data for [Fe(L-1)(H2O)(2)]Cl-2 are also reported.

First-principles analysis of electron correlation, spin ordering and phonons in the normal state of FeSe1-x

We present first-principles density-functional-theory-based calculations to determine the effects of the strength of on-site electron correlation, magnetic ordering, pressure and Se vacancies on phonon frequencies and electronic structure of FeSe1-x. The theoretical equilibrium structure (lattice parameters) of FeSe depends sensitively on the value of the Hubbard parameter U of on-site correlation and magnetic ordering. Our results suggest that there is a competition between different antiferromagnetic states due to comparable magnetic exchange couplings between first- and second-neighbor Fe sites. As a result, a short range order of stripe antiferromagnetic type is shown to be relevant to the normal state of FeSe at low temperature. We show that there is a strong spin-phonon coupling in FeSe (comparable to its superconducting transition temperature) as reflected in large changes in the frequencies of certain phonons with different magnetic ordering, which is used to explain the observed hardening of a Raman-active phonon at temperatures (similar to 100 K) where magnetic ordering sets in. The symmetry of the stripe antiferromagnetic phase permits an induced stress with orthorhombic symmetry, leading to orthorhombic strain as a secondary order parameter at the temperature of magnetic ordering. The presence of Se vacancies in FeSe gives rise to a large peak in the density of states near the Fermi energy, which could enhance the superconducting transition temperature within the BCS-like picture.

Ferromagnetic transition and specific heat of Pr(0.6)Sr(0.4)MnO(3)

The critical properties of orthorhombic Pr(0.6)Sr(0.4)MnO(3) single crystals were investigated by a series of static magnetization measurements along the three different crystallographic axes as well as by specific heat measurements. A careful range-of-fitting-analysis of the magnetization and susceptibility data obtained from the modified Arrott plots shows that Pr(0.6)Sr(0.4)MnO(3) has a very narrow critical regime. Nevertheless, the system belongs to the three-dimensional (3D) Heisenberg universality class with short-range exchange. The critical exponents obey Widom scaling and are in excellent agreement with the single scaling equation of state M(H,epsilon) = vertical bar epsilon vertical bar(beta) f(+/-)(H/vertical bar epsilon vertical bar((beta+gamma)); with f(+) for T > T(c) and f(-) for T < T(c). A detailed analysis of the specific heat that account for all relevant contributions allows us to extract and analyze the contribution related to the magnetic phase transition. The specific heat indicates the presence of a linear electronic term at low temperatures and a prominent contribution from crystal field excitations of Pr. A comparison with data from literature for PrMnO(3) shows that a Pr-Mn magnetic exchange is responsible for a sizable shift in the lowest lying excitation.

Interface-assisted spintronics: Tailoring at the molecular scale

Organic molecules adsorbed on magnetic surfaces offer the possibility to merge the concepts of molecular electronics with spintronics to build future nanoscale data storage, sensing, and computing multifunctional devices. In order to engineer the functionalities of such hybrid spintronic devices, an understanding of the electronic and magnetic properties of the interface between carbon-based aromatic materials and magnetic surfaces is essential. In this article, we discuss recent progress in the study of spin-dependent chemistry and physics associated with the above molecule-ferromagnet interface by combining state-of-the-art experiments and theoretical calculations. The magnetic properties such as molecular magnetic moment, electronic interface spin-polarization, magnetic anisotropy, and magnetic exchange coupling can be specifically tuned by an appropriate choice of the organic material and the magnetic substrate. These reports suggest a gradual shift in research toward an emerging subfield of interface-assisted molecular spintronics.

CRYSTAL-STRUCTURES AND MOSSBAUER-SPECTRA OF LAFE1-XMNXO3 AND LAFE1-XCOXO3 (X=0 TO 0.9)

The crystal structures and Mossbauer spectra of various mixed oxides LaFe1-xMnxO3 and LaFe1-xCoxO3 (x = 0 to 0.9) are determined and measured at room temperature. The results indicate that the crystal structure of both the La-Fe-Mn-O and the La-Fe-Co-O sy

Martensitic transitions and the nature of ferromagnetism in the austenitic and martensitic states of Ni-Mn-Sn alloys

Structural and magnetic transformations in the Heusler-based system Ni0.50Mn0.50¿xSnx are studied by x-ray diffraction, optical microscopy, differential scanning calorimetry, and magnetization. The structural transformations are of austenitic-martensitic character. The austenite state has an L21 structure, whereas the structures of the martensite can be 10M , 14M , or L10 depending on the Sn composition. For samples that undergo martensitic transformations below and around room temperature, it is observed that the magnetic exchange in both parent and product phases is ferromagnetic, but the ferromagnetic exchange, characteristic of each phase, is found to be of different strength. This gives rise to different Curie temperatures for the austenitic and martensitic states.

Spin reversal and magnetization jumps in ErMexMn1-xO3 perovskites (Me = Ni, Co)

The erbium-based manganite ErMnO3 has been partially substituted at the manganese site by the transition-metal elements Ni and Co. The perovskite orthorhombic structure is found from x(Ni) = 0.2-0.5 in the nickel-based solid solution ErNixMn1-xO3, while it can be extended up to x(Co) = 0.7 in the case of cobalt, provided that the synthesis is performed under oxygenation conditions to favor the presence of Co3+. Presence of different magnetic entities (i.e., Er3+, Ni2+, Co2+, Co3+, Mn3+, and Mn4+) leads to quite unusual magnetic properties, characterized by the coexistence of antiferromagnetic and ferromagnetic interactions. In ErNixMn1-xO3, a critical concentration x(crit)(Ni) = 1/3 separates two regimes: spin-canted AF interactions predominate at x < x(crit), while the ferromagnetic behavior is enhanced for x > x(crit). Spin reversal phenomena are present both in the nickel- and cobalt-based compounds. A phenomenological model based on two interacting sublattices, coupled by an antiferromagnetic exchange interaction, explains the inversion of the overall magnetic moment at low temperatures. In this model, the ferromagnetic transition-metal lattice, which orders at T-c, creates a strong local field at the erbium site, polarizing the Er moments in a direction opposite to the applied field. At low temperatures, when the contribution of the paramagnetic erbium sublattice, which varies as T-1, gets larger than the ferromagnetic contribution, the total magnetic moment changes its sign, leading to an overall ferrimagnetic state. The half-substituted compound ErCo0.50Mn0.50O3 was studied in detail, since the magnetization loops present two well-identified anomalies: an intersection of the magnetization branches at low fields, and magnetization jumps at high fields. The influence of the oxidizing conditions was studied in other compositions close to the 50/50 = Mn/Co substitution rate. These anomalies are clearly connected to the spin inversion phenomena and to the simultaneous presence of Co2+ and Co3+ magnetic moments. Dynamical aspects should be considered to well identify the high-field anomaly, since it depends on the magnetic field sweep rate. (C) 2006 Elsevier B.V. All rights reserved.

Síntese e caracterização de espécies supramoleculares de níquel(II) contendo pirazóis e pseudo-haletos com possíveis aplicações magnéticas

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Modellkomplexe zur Untersuchung der Radikal-Metall-Wechselwirkung innerhalb des wasseroxidierenden Zentrums im Photosystem II

Im Rahmen dieser Arbeit wurden zweikernige Modellkomplexe zur Untersuchung der Radikal-Metallwechselwirkung innerhalb des wasseroxidierenden Zentrums des Photo¬systems II synthetisiert und eine magneto-strukturelle Korrelation dieser Komplexe erstellt. Als Liganden wurden diverse sechs- bis siebenzähnige Chelatliganden verwendet, welche über zwei Koordinationstaschen und eine verbrückende Phenolatgruppe verfügen. Zwei daran gebundene Manganionen liegen in einer wohl definierten Umgebung nicht koordinativ gesättigt vor. An die freien Koordinationsstellen können weitere ein bis zwei Brückenliganden binden, bei denen es sich in dieser Arbeit hauptsächlich um Carboxylate handelt. Durch die Verwendung eines diamagnetischen Brückenliganden konnte die magnetische Spin-Spin-Austauschwechselwirkung zwischen den spintragenden Manganionen über die verbrücken¬de Phenolatgruppe bestimmt werden. Komplexe, welche über Manganionen in den gleichen Oxidationsstufen, aber über unterschiedliche Carboxylatbrückenliganden verfügen, weisen ähnliche magnetische Austauschwechselwirkungen zwischen den Metallzentren auf. Diese Beobachtung konnte durch eine strukturelle Ähnlichkeit dieser Komplexe erklärt werden. Mittels Aufsummieren der Bindungslängen der verbrückenden Phenolateinheit zu beiden Zentralionen kann innerhalb dieser Komplexe jeweils die Länge des Wechselwirkungspfades erhalten werden, welcher die magnetische Austauschwechselwirkung maßgeblich beein¬flusst. Je länger der Wechselwirkungspfad ist, desto kleiner ist die Austausch¬wechsel¬wirkung. Durch Austausch der diamagnetischen Carboxylate durch paramagnetische benzoat¬substituierte Nitronyl Nitroxid Radikale wurden den Komplexen ein bis zwei weitere Spinzentren hinzugefügt, welche mit den Spins der Zentralionen wechselwirken können. Simulationen der magnetischen Suszeptibilitätsmessungen liefern Werte für die magneti¬schen Austausch¬wechselwirkungen zwischen den Nitronyl Nitroxid Radikalen und den Manganionen, die in allen Fällen schwach ferromagnetisch zwischen 0 und 4,7 cm-1 sind. In einer Auftragung dieser Austauschwechselwirkungen gegen die Mangan-Carboxylat-Bindungs¬längen von strukturell charakterisierten äquivalenten acetatverbrückten Komplexen, kann eine lineare Abhängigkeit gezeigt werden.

Verknüpfung metallhaltiger Pivalatkomplexe über polyfunktionale organische Brückenliganden

Ziel der hier vorliegenden Dissertation ist es, Übergangsmetallpivalate durch gezielte Substitution monodentater Donorliganden in apikalen Positionen, unter Erhalt ihrer Grundstruktur, zu höherdimensionalen Verbindungen zu verknüpfen. Als Ausgangs-verbindungen dienen dabei [Fe3O(O2C-tBu)6(OH2)3]O2C-tBu und [Ni2(OH2)(O2C-tBu)4(HO2C-tBu)4].rnrnIm ersten Teil dieser Arbeit konnten, in Abhängigkeit der in den Reaktionen eingesetzten Liganden mit [Fe3O(O2C-tBu)6(OH2)3]O2C-tBu, symmetrisch oder asymmetrisch substituierte dreikernige Verbindungen erhalten werden. Deren strukturellen und magnetischen Eigenschaften konnten untersucht werden und die daraus resultierenden magnetostrukturellen Korrelationen auf die folgenden vorgestellten mehrkernigen bzw. höherdimensionalen Verbindungen übertragen werden, die erheblich an Komplexität zugenommen haben.rnDie 0-dimensionalen dreikernigen Einheiten zeigen, abhängig von ihren Fe-O-Bindungslängen in den µ3-Oxo verbrückten Einheiten, unterschiedlich starke antiferro-magnetische Austauschwechselwirkungen. Wenn in den Verbindungen eine längere Fe-O-Bindung und zwei kürzere Fe-O-Bindungen existieren, können diese Typ 2:a zugeordnet werden. Daraus folgt, dass die Daten der magnetischen Suszeptibilität mit zwei unterschiedlich starken Austauschwechselwirkungen (J-Kopplungen) zu simulieren sind. Es liegen eine stärkere J-Kopplung über die kurzen Fe-O-Bindungen und zwei schwächere über die lange Fe-O-Bindung vor (J1 > J2). Existieren hingegen eine kürzere Fe-O-Bindung und zwei längere Fe-O-Bindungen (Typ 2:b) sind nun die magnetischen Suszeptibilitätsdaten nur mit zwei stärkeren und einer schwächeren Kopplung zu simulieren (J1 < J2). Die vorgestellten Verbindungen zeigen alle einen Spingrundzustand S≠0, der durch konkurrierende Wechselwirkungen der Spinzentren in Dreieckssituationen begründet ist. rnDer zweite Teil der Arbeit beschäftigte sich mit dem gezielten Aufbau mehrkerniger Verbindungen, in denen die dreikernige Einheit als Grundmotiv erhalten bleiben konnte. Die Austauschwechselwirkungen der fünf- und sechskernigen Verbindungen konnten in Abhängigkeit der Bindungslängen und basierend auf den Ergebnissen der dreikernigen Einheiten aus dem ersten Teil, bestimmt werden. rnDie Synthesen der 4-Hydroxybenzaldehyd verbrückten Kettenverbindung sowie des über 3,5,3’,5’-Tetramethyl-1H,1’H-[4,4’]bipyrazolyl verknüpften 3-dimensionalen Nickelnetzwerks zeigten die erfolgreiche Umsetzung des „Bottom Up“ Ansatzes. Durch Erhaltung des jeweiligen Grundmotivs der verwendeten Ausgangsverbindung konnten die magnetischen Austauschwechselwirkungen unter Einbeziehung schwacher Wechselwirkungen durch den Raum, mit Hilfe der Theta-Weiss Temperatur, in den Simulationen bestimmt werden.rnrnDamit stellt der „Bottom Up“ Ansatz eine hervorragende Syntesestrategie für den Aufbau höherdimensionaler Verbindungen, ausgehend von zwei- bzw. dreikernigen Übergangs-metallkomplexen, dar.rn