A Molecular Ferromagnet with a Curie Temperature of 6.2 Kelvin: [Mn(C5(CH3)5)2]+[TCNQ]-

The study of magnetic phase transitions in insulating molecular solids provides new insights into mechanisms of magnetic coupling in the solid state and into critical phenomena associated with these transitions. Only a few such materials are known to display cooperative magnetic properties. The use of high-spin molecular components would enhance intermolecular spin-spin interactions and thus a series of chargetransfer (CT) salts have been synthesized that utilize the spin S = 1 molecular cation, [Mn(C(5)(CH(3))(5))(2)](+) (decamethylmanganocenium). The structure and cooperative magnetic behavior of [Mn(C(5)(CH(3))(5))(2)](+)[TCNQ(-) (decamethylmanganocenium 7,7,8,8-tetracyano-p-quinodimethanide) are reported. This salt is a bulk molecular ferromagnet with the highest critical (Curie) temperature (T(c) = 6.2 K) and coercive field (3.6 x 10(3) gauss), yet reported for such a material.     

Magnetic bistability of molecules in homogeneous solution at room temperature

Magnetic bistability, as manifested in the magnetization of ferromagnetic materials or spin crossover in transition metal complexes, has essentially been restricted to either bulk materials or to very low temperatures. We now present a molecular spin switch that is bistable at room temperature in homogeneous solution. Irradiation of a carefully designed nickel complex with blue-green light (500 nanometers) induces coordination of a tethered pyridine ligand and concomitant electronic rearrangement from a diamagnetic to a paramagnetic state in up to 75% of the ensemble. The process is fully reversible on irradiation with violet-blue light (435 nanometers). No fatigue or degradation is observed after several thousand cycles at room temperature under air. Preliminary data show promise for applications in magnetic resonance imaging.     

Direct spectroscopic detection of a zwitterionic excited state

Two electrons in two weakly coupled orbitals give rise to two states (diradical) with electrons residing in separate orbitals and two states (zwitterionic) with both electrons paired in one orbital or the other. This two-electron, two-orbital state manifold has eluded experimental confirmation because the zwitterionic states have been difficult to locate. Two-photon excitation of fluorescence from Mo(2)CI(4)(PMe(3))(4) (D2d) has been measured with linearly and circularly polarized light. From the polarization ratio and the energy of the observed transition, the 2(1)A(1) (delta*delta*) excited state has been located and characterized. In conjunction with the one-photon allowed (1)B(2) (deltadelta*) excited state, the zwitterionic state manifold for the quadruply bonded metal-metal class of compounds is thus established.     

A room-temperature molecular/organic-based magnet

The reaction of bis(benzene)vanadium with tetracyanoethylene, TCNE, affords an insoluble amorphous black solid that exhibits field-dependent magnetization and hysteresis at room temperature. The critical temperature could not be estimated as it exceeds 350 kelvin, the thermal decomposition temperature of the sample. The empirical composition of the reported material is V(TCNE)x.Y(CH(2)Cl(2)) with x approximately 2 and Y approximately 1/2. On the basis of the available magnetic and infrared data, threedimensional antiferromagnetic exchange of the donor and acceptor spins resulting in ferrimagnetic behavior appears to be the mode of magnetic coupling.     

The magnon pairing mechanism of superconductivity in cuprate ceramics

The magnon pairing mechanism is derived to explain the high-temperature superconductivity of both the La2-xSrxCu(1)O(4) and Y(1)Ba(2)Cu(3)O(7) systems. Critical features include (i) a one- or two-dimensional lattice of linear Cu-O-Cu bonds that contribute to large antiferromagnetic (superexchange) coupling of the Cu(II)(d(9)) orbitals; (ii) holes in the oxygen ppi bands [rather than Cu(III)(d(8))] leading to high mobility hole conduction; and (iii) strong ferromagnetic coupling between oxygen ppi holes and adjacent Cu(II)(d(9)) electrons. The ferromagnetic coupling of the conduction electrons with copper d spins induces the attractive interaction responsible for the superconductivity, leading to triplet-coupled pairs called "tripgems." The disordered Heisenberg lattice of antiferromagnetically coupled copper d spins serves a role analogous to the phonons in a conventional system. This leads to a maximum transition temperature of about 200 K. For La(1.85)Sr(0.15)Cu(1)O(4), the energy gap is in excellent agreement with experiment. For Y(1)Ba(2)Cu(3)O(7), we find that both the CuO sheets and the CuO chains can contribute to the supercurrent.     

Lanthanide complexes as nuclear magnetic resonance structural probes: paramagnetic anisotropy of shift reagent adducts

Magnetic anisotropy measurements on single crystals of a series of paramagnetic 8-coordinate lanthanide shift reagent adducts of the type Ln[(CH(3))(3)CCOCHCOC(CH(3))(3)(4-CH(3)C(5)H(1)N)(2) have been made for the following lanthanides: praseodymium, neodymium, samarium, europium, terbium, dysprosium, holmium, erbium, thulium, and ytterbium. The susceptibility tensors are highly anisotropic and nonaxial. Dipolar nuclear magnetic resonance shifts evaluated from the solid-state date are in satisfactory agreement with the solution results.     

Binuclear ion containing nitrogen as a bridging group

A binuclear ion ([NH(3))5RuN(2)Ru(NH(3))(5)](5)+ is formed by the direct reaction of N(2) with an aqueous solution of (NH(3))(5)RuOH(2)(2+) at room temperature. The binuclear ion is also formed by the reversible reaction of (NH(3))5RuOH(2)(2+) with (NH(3))(5)RuN(2)(2+). Solid [(NH(3))(5)RuN(2)Ru(NH(3))(5)] (BF(4))(4) has been prepared, and its ultraviolet and infrared spectra are reported.     

Dianion Stabilization by (M(C5(CH3)5)2)+: Theoretical Evidence for a Localized Ring in (DDQ)2-

Organic dianions have been stabilized by (M(C(5)(CH(3))(5))(2))(+), where M is iron or cobalt. This has allowed the structural and spectroscopic characterization of these dianions. The structure of (M(C(5)(CH(3))(5))(2))(2)(+) (DDQ)(2-), where DDQ is 2,3-dichloro-5,6-dicyanobenzoquinone, has been determined by x-ray crystallography. The structure of (DDQ)(2-)is consistent with ab initio molecular orbital calculations that suggest a localizd as opposed to a delocalized (aromatic) ring structure.     

量子点中双极化子和磁双极化子的研究进展

综述了近年来对抛物线性限制势量子点中强耦合双极化子和磁双极化子的部分研究工作.从抛物量子点中2个电子-声子体系的哈密顿量出发,采用Lee-Low-Pines-Huybrechts变分方法,研究了量子点中强耦合双极化子的振动频率、诱生势和有效势随电子-声子耦合强度、两电子相对距离和量子点半径的变化规律;采用Tokuda改进的线性组合算符法研究了温度和LO声子效应对强耦合双极化子的有效质量和平均声子数的影响.基于Lee-Low-Pines幺正变换,采用Pekar类型变分法研究了抛物量子点中强耦合磁双极化子的内部激发态性质,当考虑自旋和外磁场影响时,研究了二维量子点中强耦合磁双极化子基态的能量、声子平均数以及第一激发态的能量、声子平均数随量子点受限强度、介电常数比、电子-声子耦合强度和磁场的回旋共振频率的变化规律.     

Ferromagnetism stabilized by lattice distortion at the surface of the p-wave superconductor Sr(2)RuO(4)

Ferromagnetic (FM) spin fluctuations are believed to mediate the spin-triplet pairing for the p-wave superconductivity in Sr(2)RuO(4). Our experiments show that, at the surface, a bulk soft-phonon mode freezes into a static lattice distortion associated with an in-plane rotation of the RuO(6) octahedron. First-principle calculations confirm this structure and predict a FM ground state at the surface. This coupling between structure and magnetism in the environment of broken symmetry at the surface allows a reconsideration of the coupling mechanism in the bulk.     

Electron solvation in finite systems: femtosecond dynamics of iodide. (Water)n anion clusters

Electron solvation dynamics in photoexcited anion clusters of I-(D2O)n=4-6 and I-(H2O)4-6 were probed by using femtosecond photoelectron spectroscopy (FPES). An ultrafast pump pulse excited the anion to the cluster analog of the charge-transfer-to-solvent state seen for I- in aqueous solution. Evolution of this state was monitored by time-resolved photoelectron spectroscopy using an ultrafast probe pulse. The excited n = 4 clusters showed simple population decay, but in the n = 5 and 6 clusters the solvent molecules rearranged to stabilize and localize the excess electron, showing characteristics associated with electron solvation dynamics in bulk water. Comparison of the FPES of I-(D2O)n with I-(H2O)n indicates more rapid solvation in the H2O clusters.     

Orientational and Magnetic Ordering of Buckyballs in TDAE-C60

Spin ordering in the low-temperature magnetic phase is directly linked to the orientational ordering of C(60) molecules in organically doped fullerene derivatives. Electron spin resonance and alternating current susceptometry measurements on tetrakis(dimethylamino)ethylene-C(60) (TDAE-C(60)) (Curie temperature T(c) = 16 kelvin) show a direct coupling between spin and merohedral degrees of freedom. This coupling was experimentally demonstrated by showing that ordering the spins in the magnetic phase imprints a merohedral order on the solid or, conversely, that merohedrally ordering the C(60) molecules influences the spin order at low temperature. The merohedral disorder gives rise to a distribution of pi-lectron exchange interactions between spins on neighboring C(60) molecules, suggesting a microscopic origin for the observed spinglass behavior of the magnetic state.     

Unraveling the spin polarization of the ν = 5/2 fractional quantum Hall state

The fractional quantum Hall (FQH) effect at filling factor ν = 5/2 has recently come under close scrutiny, as its ground state may possess quasi-particle excitations obeying nonabelian statistics, a property sought for topologically protected quantum operations. However, its microscopic origin remains unknown, and candidate model wave functions include those with undesirable abelian statistics. We report direct measurements of the electron spin polarization of the ν = 5/2 FQH state using resistively detected nuclear magnetic resonance. We find the system to be fully polarized, which unambiguously rules out the most likely abelian contender and lends strong support for the ν = 5/2 state being nonabelian. Our measurements reveal an intrinsically different nature of interaction in the first excited Landau level underlying the physics at ν = 5/2.     

Spontaneous Magnetic Ordering in the Fullerene Charge-Transfer Salt (TDAE)C60

The zero-field muon spin relaxation technique has been used in the direct observation of spontaneous magnetic order below a Curie temperature (T(c)) of approximately 16.1 kelvin in the fullerene charge-transfer salt (tetrakisdimethylaminoethylene)C(60) [(TDAE)C(60)]. Coherent ordering of the electronic magnetic moments leads to a local field of 68(1) gauss at the muon site at 3.2 kelvin (parentheses indicate the error in the last digit). Substantial spatially inhomogeneous effects are manifested in the distribution of the local fields, whose width amounts to 48(2) gauss at the same temperature. The temperature evolution of the internal magnetic field below the freezing temperature mirrors that of the saturation magnetization, closely following the behavior expected for collective spin wave (magnon) excitations. The transition to a ferromagnetic state with a T(c) higher than that of any other organic material is now authenticated.     

Shattuckite and plancheite: a crystal chemical study

The orthorhombic crystal structures of shattuckite, Cu(5)( SiO(3))(4)(OH)(2) and planchétite, Cu(8)(Si(4)0(11))(2)(OH)(4) H(2)O, have been solved. Shattuckite contains silicate chains similar to pyroxene in a complex association with copper atoms, while the closely related planchéite contains silicate chains similar to amphibole.     

Time-resolved observation and control of superexchange interactions with ultracold atoms in optical lattices

Quantum mechanical superexchange interactions form the basis of quantum magnetism in strongly correlated electronic media. We report on the direct measurement of superexchange interactions with ultracold atoms in optical lattices. After preparing a spin-mixture of ultracold atoms in an antiferromagnetically ordered state, we measured coherent superexchange-mediated spin dynamics with coupling energies from 5 hertz up to 1 kilohertz. By dynamically modifying the potential bias between neighboring lattice sites, the magnitude and sign of the superexchange interaction can be controlled, thus allowing the system to be switched between antiferromagnetic and ferromagnetic spin interactions. We compare our findings to predictions of a two-site Bose-Hubbard model and find very good agreement, but are also able to identify corrections that can be explained by the inclusion of direct nearest-neighbor interactions.     

Synthesis, structure, and reactivity of an iron(V) nitride

Despite being implicated as important intermediates, iron(V) compounds have proven very challenging to isolate and characterize. Here, we report the preparation of the iron(V) nitrido complex, [PhB((t)BuIm)(3)Fe(V)≡N]BAr(F24) (PhB((t)BuIm)(3)(-) = phenyltris(3-tert-butylimidazol-2-ylidene)borato, BAr(F24) = B(3,5-(CF(3))(2)C(6)H(3))(4)(-)), by one electron oxidation of the iron(IV) nitrido precursor. Single-crystal x-ray diffraction of the iron(V) complex reveals a four-coordinate metal ion with a terminal nitrido ligand. M??bauer and electron paramagnetic resonance spectroscopic characterization, supported by electronic structure calculations, provide evidence for a d(3) iron(V) metal center in a low spin (S = 1/2) electron configuration. Low-temperature reaction of the iron(V) nitrido complex with water under reducing conditions leads to high yields of ammonia with concomitant formation of an iron(II) species.     

Topological phase transition and texture inversion in a tunable topological insulator

The recently discovered three-dimensional or bulk topological insulators are expected to exhibit exotic quantum phenomena. It is believed that a trivial insulator can be twisted into a topological state by modulating the spin-orbit interaction or the crystal lattice, driving the system through a topological quantum phase transition. By directly measuring the topological quantum numbers and invariants, we report the observation of a phase transition in a tunable spin-orbit system, BiTl(S(1-δ)Se(δ))(2), in which the topological state formation is visualized. In the topological state, vortex-like polarization states are observed to exhibit three-dimensional vectorial textures, which collectively feature a chirality transition as the spin momentum-locked electrons on the surface go through the zero carrier density point. Such phase transition and texture inversion can be the physical basis for observing fractional charge (±e/2) and other fractional topological phenomena.     

Open Framework Structures Based on Sex2- Fragments: Synthesis of (Ph4P)[M(Se6)2] (M = Ga, In, TI) in Molten (Ph4P)2Sex

Polychalcogenide compounds with open polymeric frameworks are rare, and they represent a class of compounds in which microporosity might be achieved. Microporous frameworks that are not oxide-based are now attracting interest because of the combination of catalytic and electronic properties they may simultaneously possess. Three new compounds that may be forerunners to such materials have been discovered and are reported here. The reaction of gallium (Ga), indium (In), and thallium (TI) metal with (Ph(4)P)(2)Se(5) (Ph, phenyl) and an excess of elemental selenium (Se) in a sealed, evacuated Pyrex tube at 200 degrees C yielded small red crystals of (Ph(4)P)[Ga(Se(6))(2)] (I), (Ph(4)P)[In(Se(6))(2)] (II), and (Ph(4)P)[TI(Se(6))(2)] (III), respectively. The [M(Se(6))(2)](-) (M = Ga, In, TI) ions form a two-dimensional, open framework filled with Ph(4)P(+) ions. The [M(Se(6))(2)](n)(n-) structure consists of tetrahedral M(3+) centers and bridging Se(6)(2-) ligands, leading to an extended structure in two dimensions. These layers stack perfectly one on top of the other giving rise to one-dimensional channels running down the c axis that are filled with Ph(4)P(+) cations. These cations are situated in the layers, as opposed to between the layers, and the whole structure can be viewed as a template. Compound II shows remarkable thermal stability and melts congruently at 242 degrees C. Upon cooling to room temperature it gives a glassy phase that recrystallizes upon subsequent heating to 160 degrees C.     

Spin-polarized light-emitting diode based on an organic bipolar spin valve

The spin-polarized organic light-emitting diode (spin-OLED) has been a long-sought device within the field of organic spintronics. We designed, fabricated, and studied a spin-OLED with ferromagnetic electrodes that acts as a bipolar organic spin valve (OSV), based on a deuterated derivative of poly(phenylene-vinylene) with small hyperfine interaction. In the double-injection limit, the device shows ~1% spin valve magneto-electroluminescence (MEL) response, which follows the ferromagnetic electrode coercive fields and originates from the bipolar spin-polarized space charge-limited current. In stark contrast to the response properties of homopolar OSV devices, the MEL response in the double-injection device is practically independent of bias voltage, and its temperature dependence follows that of the ferromagnetic electrode magnetization. Our findings provide a pathway for organic displays controlled by external magnetic fields.