Noncontact Layer Stabilization of Azafullerene Radicals: Route toward High-Spin-Density Surfaces.

We deposit azafullerene C59N• radicals in a vacuum on the Au(111) surface for layer thicknesses between 0.35 and 2.1 monolayers (ML). The layers are characterized using X-ray photoemission (XPS) and X-ray absorption fine structure (NEXAFS) spectroscopy, low-temperature scanning tunneling microscopy (STM), and by density functional calculations (DFT). The singly unoccupied C59N orbital (SUMO) has been identified in the N 1s NEXAFS/XPS spectra of C59N layers as a spectroscopic fingerprint of the molecular radical state. At low molecular coverages (up to 1 ML), films of monomeric C59N are stabilized with the nonbonded carbon orbital neighboring the nitrogen oriented toward the Au substrate, whereas in-plane intermolecular coupling into diamagnetic (C59N)2 dimers takes over toward the completion of the second layer. By following the C59N• SUMO peak intensity with increasing molecular coverage, we identify an intermediate high-spin-density phase between 1 and 2 ML, where uncoupled C59N• monomers in the second layer with pronounced radical character are formed. We argue that the C59N• radical stabilization of this supramonolayer phase of monomers is achieved by suppressed coupling to the substrate. This results from molecular isolation on top of the passivating azafullerene contact layer, which can be explored for molecular radical state stabilization and positioning on solid substrates.

The Role of Lattice Defects on the Optical Properties of TiO2 Nanotube Arrays for Synergistic Water Splitting.

In this study, we report a facile one-step chemical method to synthesize reduced titanium dioxide (TiO2) nanotube arrays (NTAs) with point defects. Treatment with NaBH4 introduces oxygen vacancies (OVs) in the TiO2 lattice. Chemical analysis and optical studies indicate that the OV density can be significantly increased by changing reduction time treatment, leading to higher optical transmission of the TiO2 NTAs and retarded carrier recombination in the photoelectrochemical process. A cathodoluminescence (CL) study of reduced TiO2 (TiO2-x) NTAs revealed that OVs contribute significantly to the emission bands in the visible range. It was found that the TiO2 NTAs reduced for a longer duration exhibited a higher concentration of OVs. A typical CL spectrum of TiO2 was deconvoluted to four Gaussian components, assigned to F, F+, and Ti3+ centers. X-ray photoelectron spectroscopy measurements were used to support the change in the surface chemical bonding and electronic valence band position in TiO2. Electron paramagnetic resonance spectra confirmed the presence of OVs in the TiO2-x sample. The prepared TiO2-x NTAs show an enhanced photocurrent for water splitting due to pronounced light absorption in the visible region, enhanced electrical conductivity, and improved charge transportation.

Robust coherent spin centers from stable azafullerene radicals entrapped in cycloparaphenylene rings.

Molecular entities with robust spin-1/2 are natural two-level quantum systems for realizing qubits and are key ingredients of emerging quantum technologies such as quantum computing. Here we show that robust and abundant spin-1/2 species can be created in situ in the solid state from spin-active azafullerene C59N cages supramolecularly hosted in crystals of [10]cycloparaphenylene ([10]CPP) nanohoops. This is achieved via a two-stage thermally-assisted homolysis of the parent diamagnetic [10]CPP⊃(C59N)2⊂[10]CPP supramolecular complex. Upon cooling, the otherwise unstable C59N˙ radical is remarkably persistent with a measured radical lifetime of several years. Additionally, pulsed electron paramagnetic resonance measurements show long coherence times, fulfilling a basic condition for any qubit manipulation, and observed Rabi oscillations demonstrate single qubit operation. These findings together with rapid recent advances on the synthesis of carbon nanohoops offer the potential to fabricate tailored cycloparaphenylene networks hosting C59N˙ centers, providing a promising platform for building complex qubit circuits.

Crystal Structure and Stoichiometric Composition of Potassium-Intercalated Tetracene.

The products of the solid-state reactions between potassium metal and tetracene (K:Tetracene, 1:1, 1.5:1, and 2:1) are fully structurally characterized. Synchrotron X-ray powder diffraction shows that only K2Tetracene forms under the reaction conditions studied, with unreacted tetracene always present for x < 2. Diffraction and 13C MAS NMR show that K2Tetracene has a crystal structure that is analogous to that of K2Pentacene, but with the cations ordered on two sites because of the influence of the length of the hydrocarbon on possible cation positions. K2Tetracene is a nonmagnetic insulator, thus further questioning the nature of reported superconductivity in this class of materials.

A Long-Lived Azafullerenyl Radical Stabilized by Supramolecular Shielding with a [10]Cycloparaphenylene.

A major handicap towards the exploitation of radicals is their inherent instability. In the paramagnetic azafullerenyl radical C59 N. , the unpaired electron is strongly localized next to the nitrogen atom, which induces dimerization to diamagnetic bis(azafullerene), (C59 N)2 . Conventional stabilization by introducing steric hindrance around the radical is inapplicable here because of the concave fullerene geometry. Instead, we developed an innovative radical shielding approach based on supramolecular complexation, exploiting the protection offered by a [10]cycloparaphenylene ([10]CPP) nanobelt encircling the C59 N. radical. Photoinduced radical generation is increased by a factor of 300. The EPR signal showing characteristic 14 N hyperfine splitting of C59 N. ⊂ [10]CPP was traced even after several weeks, which corresponds to a lifetime increase of >108 . The proposed approach can be generalized by tuning the diameter of the employed nanobelts, opening new avenues for the design and exploitation of radical fullerenes.

Unraveling the Arrangement of Al and Fe within the Framework Explains the Magnetism of Mixed-Metal MIL-100(Al,Fe).

Properties of mixed-metal MOFs depend on the distribution of different metals within their frameworks. Determination of this distribution is often very challenging. Using an example of aluminum- and iron-containing MIL-100, we demonstrate that 27Al NMR spectroscopy, when combined with first-principles calculations and magnetic, X-band electron paramagnetic resonance, Fe K-edge extended X-ray absorption fine structure, and Mössbauer measurements, enables one to accurately determine the arrangement of Al and Fe within the metal trimers, which are the basic building units of MIL-100. In this particular material, the incorporation of Fe and Al on the framework metal sites is random. Crucial for deciphering the arrangement is detecting NMR signals, shifted because of the strong hyperfine interaction between the 27Al nuclei and the unpaired electronic spins of Fe3+ ions, assigning the shifted signals aided by first-principles calculations of hyperfine couplings, and quantitatively evaluating the NMR intensities and the measured effective magnetic moment.

Verwey-type charge ordering transition in an open-shell p-electron compound.

The Verwey transition in Fe3O4, a complex structural phase transition concomitant with a jump in electrical conductivity by two orders of magnitude, has been a benchmark for charge ordering (CO) phenomena in mixed-valence transition metal materials. CO is of central importance, because it frequently competes with functional properties such as superconductivity or metallic ferromagnetism. However, the CO state in Fe3O4 turned out to be complex, and the mechanism of the Verwey transition remains controversial. We demonstrate an archetypical Verwey-type transition in an open p-shell anionic mixed-valence compound using complementary diffraction and spectroscopic techniques. In Cs4O6, a phase change from a cubic structure with a single crystallographic site for the molecular O2x- building units to a tetragonal structure with ordered superoxide O2- and peroxide O22- entities is accompanied by a drastic drop in electronic conductivity and molecular charge fluctuation rates. The simple CO pattern of molecular units and the lack of magnetic order suggest Cs4O6 as a model system for disentangling the complex interplay of charge, lattice, orbital, and spin degrees of freedom in Verwey-type CO processes.

π-electron S = ½ quantum spin-liquid state in an ionic polyaromatic hydrocarbon.

Molecular solids with cooperative electronic properties based purely on π electrons from carbon atoms offer a fertile ground in the search for exotic states of matter, including unconventional superconductivity and quantum magnetism. The field was ignited by reports of high-temperature superconductivity in materials obtained by the reaction of alkali metals with polyaromatic hydrocarbons, such as phenanthrene and picene, but the composition and structure of any compound in this family remained unknown. Here we isolate the binary caesium salts of phenanthrene, Cs(C14H10) and Cs2(C14H10), to show that they are multiorbital strongly correlated Mott insulators. Whereas Cs2(C14H10) is diamagnetic because of orbital polarization, Cs(C14H10) is a Heisenberg antiferromagnet with a gapped spin-liquid state that emerges from the coupled highly frustrated Δ-chain magnetic topology of the alternating-exchange spiral tubes of S = ½ (C14H10)•- radical anions. The absence of long-range magnetic order down to 1.8 K (T/J ≈ 0.02; J is the dominant exchange constant) renders the compound an excellent candidate for a spin-½ quantum-spin liquid (QSL) that arises purely from carbon π electrons.

Atomic motions in the layered copper pseudochalcogenide CuNCN indicative of a quantum spin-liquid scenario.

We explore the thermodynamic properties of the layered copper(II) carbodiimide CuNCN by heat-capacity measurements and investigate the corresponding thermal atomic motions by means of neutron powder diffraction as well as inelastic neutron scattering. The experiments are complemented by a combination of density-functional calculations, phonon analysis and analytic theory. The existence of a soft flexural mode-bending of the layers, characteristic for the material structure-is established in the phonon spectrum of CuNCN by giving characteristic temperature-dependent contributions to the heat capacity and atomic displacement parameters. The agreement with the neutron data allows us to extract a residual-on top of the lattice-presumably spinon contribution to the heat capacity [Formula: see text], speaking in favor of the spin-liquid picture of the electronic phases of CuNCN.

Metal-to-insulator crossover in alkali doped zeolite.

We report a systematic nuclear magnetic resonance investigation of the (23)Na spin-lattice relaxation rate, 1/T1, in sodium loaded low-silica X (LSX) zeolite, Nan/Na12-LSX, for various loading levels of sodium atoms n across the metal-to-insulator crossover. For high loading levels of n ≥ 14.2, 1/T1T shows nearly temperature-independent behaviour between 10 K and 25 K consistent with the Korringa relaxation mechanism and the metallic ground state. As the loading levels decrease below n ≤ 11.6, the extracted density of states (DOS) at the Fermi level sharply decreases, although a residual DOS at Fermi level is still observed even in the samples that lack the metallic Drude-peak in the optical reflectance. The observed crossover is a result of a complex loading-level dependence of electric potential felt by the electrons confined to zeolite cages, where the electronic correlations and disorder both play an important role.

Optimized unconventional superconductivity in a molecular Jahn-Teller metal.

Understanding the relationship between the superconducting, the neighboring insulating, and the normal metallic state above T c is a major challenge for all unconventional superconductors. The molecular A3C60 fulleride superconductors have a parent antiferromagnetic insulator in common with the atom-based cuprates, but here, the C60 (3-) electronic structure controls the geometry and spin state of the structural building unit via the on-molecule Jahn-Teller effect. We identify the Jahn-Teller metal as a fluctuating microscopically heterogeneous coexistence of both localized Jahn-Teller-active and itinerant electrons that connects the insulating and superconducting states of fullerides. The balance between these molecular and extended lattice features of the electrons at the Fermi level gives a dome-shaped variation of T c with interfulleride separation, demonstrating molecular electronic structure control of superconductivity.

Controlling Disorder and Superconductivity in Titanium Oxynitride Nanoribbons with Anion Exchange.

In recent years, conversion chemical reactions, which are driven by ion diffusion, emerged as an important concept for formation of nanoparticles. Here we demonstrate that the slow anion diffusion in anion exchange reactions can be efficiently used to tune the disorder strength and the related electronic properties of nanoparticles. This paradigm is applied to high-temperature formation of titanium oxynitride nanoribbons, Ti(O,N), transformed from hydrogen titanate nanoribbons in an ammonia atmosphere. The nitrogen content, which determines the chemical disorder through random O/N occupancy and ion vacancies in the Ti(O,N) composition, increases with the reaction time. The presence of disorder has paramount effects on resistivity of Ti(O,N) nanoribbons. Atypically for metals, the resistivity increases with decreasing temperature due to the weak localization effects. From this state, superconductivity develops below considerably or completely suppressed critical temperatures, depending on the disorder strength. Our results thus establish the remarkable versatility of anion exchange for tuning of the electronic properties of Ti(O,N) nanoribbons and suggest that similar strategies may be applied to a vast number of nanostructures.

Size and symmetry of the superconducting gap in the f.c.c. Cs3C60 polymorph close to the metal-Mott insulator boundary.

The alkali fullerides, A(3)C(60) (A = alkali metal) are molecular superconductors that undergo a transition to a magnetic Mott-insulating state at large lattice parameters. However, although the size and the symmetry of the superconducting gap, Δ, are both crucial for the understanding of the pairing mechanism, they are currently unknown for superconducting fullerides close to the correlation-driven magnetic insulator. Here we report a comprehensive nuclear magnetic resonance (NMR) study of face-centred-cubic (f.c.c.) Cs(3)C(60) polymorph, which can be tuned continuously through the bandwidth-controlled Mott insulator-metal/superconductor transition by pressure. When superconductivity emerges from the insulating state at large interfullerene separations upon compression, we observe an isotropic (s-wave) Δ with a large gap-to-superconducting transition temperature ratio, 2Δ0/k(B)T(c) = 5.3(2) [Δ0 = Δ(0 K)]. 2Δ0/k(B)T(c) decreases continuously upon pressurization until it approaches a value of ~3.5, characteristic of weak-coupling BCS theory of superconductivity despite the dome-shaped dependence of Tc on interfullerene separation. The results indicate the importance of the electronic correlations for the pairing interaction as the metal/superconductor-insulator boundary is approached.

Solvothermal and surfactant-free synthesis of crystalline Nb(2)O(5), Ta(2)O(5), HfO(2), and Co-doped HfO(2) nanoparticles.

A simple route to niobium, hafnium and tantalum oxide nanocrystals using a nonaqueous sol-gel route based on the solvothermal reaction of the corresponding metal chlorides with benzyl alcohol is presented. This approach can easily be extended to the preparation of high quality Co-doped HfO(2) nanoparticles of uniform size and shape and with a homogenous distribution of the magnetic ions. The structural characterization of all these nanomaterials as well as the magnetic properties of pure and doped hafnia, with special attention to the doping efficiency, are discussed. The obtained Co-doped hafnia exhibits paramagnetic properties with very weak antiferromagnetic interactions between Co ions moments.

Co-Doped ZnO nanoparticles: minireview.

Diluted magnetic semiconductors with a Curie temperature exceeding 300 K are promising candidates for spintronic devices and spin-based electronic technologies. We review recent achievements in the field of one of them: Co-doped ZnO at the nanoparticulate scale.

Polymorphism control of superconductivity and magnetism in Cs(3)C(60) close to the Mott transition.

The crystal structure of a solid controls the interactions between the electronically active units and thus its electronic properties. In the high-temperature superconducting copper oxides, only one spatial arrangement of the electronically active Cu(2+) units-a two-dimensional square lattice-is available to study the competition between the cooperative electronic states of magnetic order and superconductivity. Crystals of the spherical molecular C(60)(3-) anion support both superconductivity and magnetism but can consist of fundamentally distinct three-dimensional arrangements of the anions. Superconductivity in the A(3)C(60) (A = alkali metal) fullerides has been exclusively associated with face-centred cubic (f.c.c.) packing of C(60)(3-) (refs 2, 3), but recently the most expanded (and thus having the highest superconducting transition temperature, T(c); ref. 4) composition Cs(3)C(60) has been isolated as a body-centred cubic (b.c.c.) packing, which supports both superconductivity and magnetic order. Here we isolate the f.c.c. polymorph of Cs(3)C(60) to show how the spatial arrangement of the electronically active units controls the competing superconducting and magnetic electronic ground states. Unlike all the other f.c.c. A(3)C(60) fullerides, f.c.c. Cs(3)C(60) is not a superconductor but a magnetic insulator at ambient pressure, and becomes superconducting under pressure. The magnetic ordering occurs at an order of magnitude lower temperature in the geometrically frustrated f.c.c. polymorph (Néel temperature T(N) = 2.2 K) than in the b.c.c.-based packing (T(N) = 46 K). The different lattice packings of C(60)(3-) change T(c) from 38 K in b.c.c. Cs(3)C(60) to 35 K in f.c.c. Cs(3)C(60) (the highest found in the f.c.c. A(3)C(60) family). The existence of two superconducting packings of the same electronically active unit reveals that T(c) scales universally in a structure-independent dome-like relationship with proximity to the Mott metal-insulator transition, which is governed by the role of electron correlations characteristic of high-temperature superconducting materials other than fullerides.

Strong correlations in highly electron-doped Zn(II)-DNA complexes.

We present spectroscopic measurements on the first example of a chemically electron-doped metal-DNA complex. We show that a doping level as high as the stoichiometric limit of one electron per base pair can be achieved. The doped unpaired electrons occupy lowest unoccupied molecular orbital levels of the nucleobases as detected with electron spin resonance and x-ray absorption near edge structure measurements. Delocalization and strong correlations between the unpaired electrons are evident from a temperature-independent spin susceptibility and a microwave conductivity above 100 K.

MnO(x) nanoparticles supported on a new mesostructured silicate with textural porosity.

A two-step synthesis of a novel mesostructured silicate, KIL-2, and its manganese-containing analogue, Mn/KIL-2, has been developed. KIL-2 possesses interparticle mesopores with pore dimensions between 5 and 60 nm and a surface area of 448 m(2). The mesopores are formed by the aggregation of silica nanoparticles, which creates a network with interparticle voids. The particle size and the pore diameters depend on the temperature of the ageing step (first step) and on the solvothermal treatment in ethanol (second step), respectively. Mn/KIL-2 contains octahedrally coordinated Mn(3+) (80%) and tetrahedrally coordinated Mn(2+) (20%) ions. Mn(3+) ions are present in the extra-framework MnO(x) nanoparticles with typical dimensions of 2 nm, which are homogeneously distributed throughout the material. Mn(2+) ions occur as isolated manganese framework sites. The material is also able to retain its structure characteristics after the hydrothermal treatment in boiling water. Because of its non-toxic nature and cost-effective synthesis, Mn/KIL-2 thus exhibits properties that are needed for an environment-friendly catalyst.

The disorder-free non-BCS superconductor Cs3C60 emerges from an antiferromagnetic insulator parent state.

The body-centered cubic A15-structured cesium fulleride Cs3C60 is not superconducting at ambient pressure and is free from disorder, unlike the well-studied face-centered cubic A3C60 alkali metal fulleride superconductors. We found that in Cs3C60, where the molecular valences are precisely assigned, the superconducting state at 38 kelvin emerges directly from a localized electron antiferromagnetic insulating state with the application of pressure. This transition maintains the threefold degeneracy of the active orbitals in both competing electronic states; it is thus a purely electronic transition to a superconducting state, with a dependence of the transition temperature on pressure-induced changes of anion packing density that is not explicable by Bardeen-Cooper-Schrieffer (BCS) theory.

Oxygen self-doping in hollandite-type vanadium oxyhydroxide nanorods.

A nonaqueous liquid-phase route involving the reaction of vanadium oxychloride with benzyl alcohol leads to the formation of single-crystalline and semiconducting VO 1.52(OH) 0.77 nanorods with an ellipsoidal morphology, up to 500 nm in length and typically about 100 nm in diameter. Composition, structure, and morphology were thoroughly analyzed by neutron and synchrotron powder X-ray diffraction as well as by different electron microscopy techniques (SEM, (HR)TEM, EDX, and SAED). The data obtained point to a hollandite-type structure which, unlike other vanadates, contains oxide ions in the channels along the c-axis, with hydrogen atoms attached to the edge-sharing oxygen atoms, forming OH groups. According to structural probes and magnetic measurements (1.94 mu B/V), the formal valence of vanadium is +3.81 (V (4+)/V (3+) atomic ratio approximately 4). The experimentally determined density of 3.53(5) g/cm (3) is in good agreement with the proposed structure and nonstoichiometry. The temperature-dependent DC electrical conductivity exhibits Arrhenius-type behavior with a band gap of 0.64 eV. The semiconducting behavior is interpreted in terms of electron hopping between vanadium cations of different valence states (small polaron model). Ab initio density-functional calculations with a local spin density approximation including orbital potential (LSDA + U with an effective U value of 4 eV) have been employed to extract the electronic structure. These calculations propose, on the one hand, that the electronic conductivity is based on electron hopping between neighboring V (3+) and V (4+) sites, and, on the other hand, that the oxide ions in the channels act as electron donors, increasing the fraction of V (3+) cations, and thus leading to self-doping. Experimental and simulated electron energy-loss spectroscopy data confirm both the presence of V (4+) and the validity of the density-of-states calculation. Temperature-dependent magnetic susceptibility measurements indicate strongly frustrated antiferromagnetic interactions between the vanadium ions. A model involving the charge order of the V (3+) sites is proposed to account for the observed formation of the magnetic moment below 25 K.