Layer-Dependent Interfacial Transport and Optoelectrical Properties of MoS2 on Ultraflat Metals.

Layered materials based on transition-metal dichalcogenides (TMDs) are promising for a wide range of electronic and optoelectronic devices. Realizing such practical applications often requires metal-TMD connections or contacts. Hence, a complete understanding of electronic band alignments and potential barrier heights governing the transport through metal-TMD junctions is critical. However, it is presently unclear how the energy bands of a TMD align while in contact with a metal as a function of the number of layers. In pursuit of removing this knowledge gap, we have performed conductive atomic force microscopy (CAFM) of few-layered (1 to 5 layers) MoS2 immobilized on ultraflat conducting Au surfaces [root-mean-square (rms) surface roughness < 0.2 nm] and indium-tin oxide (ITO) substrates (rms surface roughness < 0.7 nm) forming a vertical metal (CAFM tip)-semiconductor-metal device. We have observed that the current increases with the number of layers up to five layers. By applying Fowler-Nordheim tunneling theory, we have determined the barrier heights for different layers and observed how this barrier decreases as the number of layers increases. Using density functional theory calculations, we successfully demonstrated that the barrier height decreases as the layer number increases. By illuminating TMDs on a transparent ultraflat conducting ITO substrate, we observed a reduction in current when compared to the current measured in the dark, hence demonstrating negative photoconductivity. Our study provides a fundamental understanding of the local electronic and optoelectronic behaviors of the TMD-metal junction, which depends on the numbers of TMD layers and may pave an avenue toward developing nanoscale electronic devices with tailored layer-dependent transport properties.

Nonlinear Self-Action of Light through Biological Suspensions.

It is commonly thought that biological media cannot exhibit an appreciable nonlinear optical response. We demonstrate, for the first time to our knowledge, a tunable optical nonlinearity in suspensions of cyanobacteria that leads to robust propagation and strong self-action of a light beam. By deliberately altering the host environment of the marine bacteria, we show experimentally that nonlinear interaction can result in either deep penetration or enhanced scattering of light through the bacterial suspension, while the viability of the cells remains intact. A theoretical model is developed to show that a nonlocal nonlinearity mediated by optical forces (including both gradient and forward-scattering forces) acting on the bacteria explains our experimental observations.

The chemical biology of the persulfide (RSSH)/perthiyl (RSS·) redox couple and possible role in biological redox signaling.

The recent finding that hydropersulfides (RSSH) are biologically prevalent in mammalian systems has prompted further investigation of their chemical properties in order to provide a basis for understanding their potential functions, if any. Hydropersulfides have been touted as hyper-reactive thiol-like species that possess increased nucleophilicity and reducing capabilities compared to their thiol counterparts. Herein, using persulfide generating model systems, the ability of RSSH species to act as one-electron reductants has been examined. Not unexpectedly, RSSH is relatively easily oxidized, compared to thiols, by weak oxidants to generate the perthiyl radical (RSS·). Somewhat surprisingly, however, RSS· was found to be stable in the presence of both O2 and NO and only appears to dimerize. Thus, the RSSH/RSS· redox couple is readily accessible under biological conditions and since dimerization of RSS· may be a rare event due to low concentrations and/or sequestration within a protein, it is speculated that the general lack of reactivity of individual RSS· species may allow this couple to be utilized as a redox component in biological systems.

Voltage clustering in redox-active ligand complexes: mitigating electronic communication through choice of metal ion.

The redox-active bis(imino)acenapthene (BIAN) ligand was used to synthesize homoleptic aluminum, chromium, and gallium complexes of the general formula (BIAN)3M. The resulting compounds were characterized using X-ray crystallography, NMR, EPR, magnetic susceptibility and cyclic voltammetry measurements and modeled using both DFT and ab initio wavefunction calculations to compare the orbital contributions of main group elements and transition metals in ligand-based redox events. Complexes of this type have the potential to improve the energy density and electrolyte stability of grid-scale energy storage technologies, such as redox flow batteries, through thermodynamically-clustered redox events.

Oxidation of Electron Donor-Substituted Verdazyls: Building Blocks for Molecular Switches.

Species that can undergo changes in electronic configuration as a result of an external stimulus such as pH or solvent polarity can play an important role in sensors, conducting polymers, and molecular switches. One way to achieve such structures is to couple two redox-active fragments, where the redox activity of one of them is strongly dependent upon environment. We report on two new verdazyls, one subsituted with a di-tert-butyl phenol group and the other with a dimethylaminophenyl group, that have the potential for such behavior upon oxidation. Oxidation of both verdazyls with copper(II) triflate in acetonitrile gives diamagnetic verdazylium ions characterized by NMR and UV-vis spectroscopies. Deprotonation of the phenol-verdazylium results in electron transfer and a switch from a singlet state to a paramagnetic triplet diradical identified by electron spin resonance. The dimethylaminoverdazylium 9 has a diamagnetic ground state, in line with predictions from simple empirical methods and supported by density functional theory calculations. These results indicate that verdazyls may complement nitroxides as spin carriers in the design of organic molecular electronics.

Brine assemblages of ultrasmall microbial cells within the ice cover of Lake Vida, Antarctica.

The anoxic and freezing brine that permeates Lake Vida's perennial ice below 16 m contains an abundance of very small (≤0.2-µm) particles mixed with a less abundant population of microbial cells ranging from >0.2 to 1.5 µm in length. Fluorescent DNA staining, electron microscopy (EM) observations, elemental analysis, and extraction of high-molecular-weight genomic DNA indicated that a significant portion of these ultrasmall particles are cells. A continuous electron-dense layer surrounding a less electron-dense region was observed by EM, indicating the presence of a biological membrane surrounding a cytoplasm. The ultrasmall cells are 0.192 ± 0.065 µm, with morphology characteristic of coccoid and diplococcic bacterial cells, often surrounded by iron-rich capsular structures. EM observations also detected the presence of smaller unidentified nanoparticles of 0.020 to 0.140 µm among the brine cells. A 16S rRNA gene clone library from the brine 0.1- to 0.2-µm-size fraction revealed a relatively low-diversity assemblage of Bacteria sequences distinct from the previously reported >0.2-µm-cell-size Lake Vida brine assemblage. The brine 0.1- to 0.2-µm-size fraction was dominated by the Proteobacteria-affiliated genera Herbaspirillum, Pseudoalteromonas, and Marinobacter. Cultivation efforts of the 0.1- to 0.2-µm-size fraction led to the isolation of Actinobacteria-affiliated genera Microbacterium and Kocuria. Based on phylogenetic relatedness and microscopic observations, we hypothesize that the ultrasmall cells in Lake Vida brine are ultramicrocells that are likely in a reduced size state as a result of environmental stress or life cycle-related conditions.

Direct Synthesis of Anatase Films with ~100% (001) Facets and [001] Preferred Orientation.

Anatase films exhibiting ~100% (001) reactive facets at the surface were grown hydrothermally on gold substrate from a homogeneous solution of TiF(4) and NaF. In addition to NaF, it was found that TiO(2) films with very similar properties could be prepared with the fluoride salts LiF, CsF, HF, NH(4)F, and N(CH(2)CH(3))(4)F. The polycrystalline anatase films are continuous, approximately 1 µm thick, and evenly coat the substrate. The surface grain size is ~400 nm. Grazing angle XRD measurements show that the films exhibit a high degree of preferred orientation with the c-axis normal to the substrate surface. SEM images reveal that the grains span the thickness of the films. Annealing the films at 500 °C removes fluorine and causes crystallites within the grains to restructure as shown by SEM, XRD, and Raman spectroscopy. Supported anatase films grown from this one-pot method may serve as oxidative photocatalysts and electrodes for photoelectrochemical applications such as solar cells and hydrogen evolution.

Building blocks for molecule-based magnets: radical anions and dianions of substituted 3,6-dimethylenecyclohexane-1,2,4,5-tetrones as paramagnetic bridging ligands.

We have prepared four tetraaryl derivatives of 3,6-dimethylene-1,2,4,5-tetraoxocyclohexane (aryl = Ph; 4-MeOPh; 4-Me(2)NPh; and 3,5-(t-Bu)(2)-4-MeOPh) with guidance from an earlier reported ab initio analysis (Misiolek, A. W.; Jackson, J. E. J. Am. Chem. Soc. 2001, 123, 4774-4780). These electron acceptors may be chemically or electrochemically reduced to the mono- and dianions desired as building blocks for the assembly of molecule-based magnets. Cyclic voltammetry shows that the potential of the first reduction wave depends on the electron donor ability of the aryl ring substituents, ranging from -0.28 V for the tetraphenyl derivative to -0.78 V for the p-dimethylamino substituted analogue (vs ferrocene/ferrocinium(+) at 0.46 V). Spin density distributions in the semiquinone moieties were elucidated by electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) observations of hyperfine couplings to internal (1)H sites and bound alkali metal cations. X-ray diffraction studies of the sodium and potassium salts of the octa-t-butyltetramethoxy derivative reveal the structure of the monoanion and its tendency to self-assemble with metal cations into one-dimensional chains in the solid state. Within the chains the anions display the expected bridging and chelating mode of coordination; SQUID magnetometry revealed weak intermolecular spin-spin couplings of 2J = -0.2 and approximately 0 K for the sodium and potassium salts, respectively. NIR transitions in the electronic spectra of the monoanions in solution are consistent with the expected low energy gap between frontier orbitals and its tunability by substituent variations. EPR studies of the free dianions and monoradical analogues indicate diradical localization into separate triphenylmethyl-like monoradicals via twisting of the diarylmethylene termini.

Tripod self-assembled monolayer on Au(111) prepared by reaction of hydroxyl-terminated alkylthiols with SiCl4.

Infrared reflection spectroscopy (IRS), single wavelength ellipsometry, and density functional theory were used to elucidate the structure of a molecular tripod self-assembled monolayer (SAM) on polycrystalline gold{111} substrates. The tripod SAM was formed by the reaction of SiCl4 with a densely packed monolayer of 2-mercaptoethanol, 6-mercaptohexanol, and 16-mercaptohexadecanol under inert atmosphere. After reaction with SiCl4, IRS spectra show an intense absorption at approximately 1112 cm(-1) that is attributed to Si-O-C asymmetric stretching vibration of a molecular tripod structure. Harmonic vibrational frequencies computed at the B3LYP/6-311+g** level of theory for the mercaptoethanol tripod SAM closely match the experimental IRS spectra, giving further support for the tripod structure. When rinsed with methanol or water, the Si-Cl-terminated SAM becomes capped with Si-OMe or Si-OH. The silanol-terminated tripod SAM is expected to find use in the preparation of thin zeolite and silica films on gold substrates.

One-dimensional zigzag chains of Cs-: the structures and properties of Li+ (cryptand[2.1.1])Cs- and Cs+ (cryptand[2.2.2])Cs-.

The crystal structure and properties of lithium (cryptand[2.1.1]) ceside, Li+ (C211)Cs-, are reported. Li+ (C211)Cs- is the second ceside and third alkalide with a one-dimensional (1D) zigzag chain of alkali metal anions. The distance between adjacent Cs- anions, 6 A, is shorter than the sum of the van der Waals radii, 7 A. Optical, magic angle spinning NMR, two-probe alternating and direct current conductivity, and electron paramagnetic resonance measurements reveal unique physical properties that result from the overlap of adjacent Cs- wave functions in the chain structure. The properties of cesium (cryptand[2.2.2]) ceside, Cs+ (C222)Cs-, were also studied to compare the effects of the subtle geometric changes between the two 1D zigzag chain structures. Li+ (C211)Cs- and Cs+ (C222)Cs- are both low-band-gap semiconductors with anisotropic reflectivities and large paramagnetic 133Cs NMR chemical shifts relative to Cs- (g). An electronic structure model consistent with the experimental data has sp2-hybridized Cs- within the chain and sp-hybridized chain ends. Ab initio multiconfiguration self-consistent field calculations on the ceside trimer, Cs3(3-), support this model and indicate a net bonding interaction between nearest neighbors. The buildup of electron density between adjacent Cs- anions is visualized through an electron density difference map constructed by subtracting the density of three cesium atoms from the short Cs3(3-) fragment.

Intramolecular pi-dimerization in a 1,1'-bis(verdazyl)ferrocene diradical.

The solid state structure of 1,1'-bis(verdazyl)ferrocene reveals the two radical moieties associated intramolecularly to give the first example of a pi-dimer of a stable verdazyl radical. The pi-dimer structure is not maintained in solution. Magnetic characterization indicates that the radicals are sufficiently strongly antiferromagnetically coupled so as to render the molecule diamagnetic at room temperature.

Structural and magnetic properties of vanadyl dichloride solvates: from molecular units to extended hydrogen-bonded solids.

The preparation, structural characterization and magnetic properties of three solvent adducts of VOCl(2), trans-VOCl(2)(THF)(2)(H(2)O) (1), trans-VOCl(2)(H(2)O)(2).2Et(2)O (2) and cis-VOCl(2)(MeOH)(3) (3) are described. In these solids, hydrogen bonding among the inorganic complexes is the critical determinant of the formation of extended magnetic networks. Compound forms one-dimensional double chains where alternating monomers from the two branches of the chain are hydrogen bonded via the V-Cl ... H-O-V network (with an axial water molecule and equatorial chloride ions). Magnetic studies indicate no interaction among the vanadyl centers. The paramagnetism of 1 is consistent with the extension of the network from the hydrogen donor site of the axial water, which is orthogonal to the d(xy) magnetic orbital. Compound 2 forms one-dimensional chains with water molecules of adjacent monomers held together by hydrogen bonds to ether molecules (V-O-H ... O(ether) ... H -O-V). The chain network radiates only through the equatorial plane of the complex where the water molecules are located. The presence of the intervening solvent molecule between hydrogen bonds of the primary coordination sphere magnetically insulates metal centers and compound is also a simple paramagnet. Removal of the solvent turns on the magnetic interaction and neighboring spin centers couple antiferromagnetically. Compound 3 forms a layered structure via V-Cl ... H-O-V hydrogen bonding, where all the hydrogen donor sites participate in the formation of the network. The vanadyl spin centers, at distances of 5.5 and 6.5 A from each other, couple antiferromagnetically (J/k=-0.7 K). Thus, magnetic coupling among metal centers is achieved when the hydrogen bond network directly radiates from the coordination plane containing the magnetic orbital. These results further support the utility of hydrogen bond as a viable design element in the construction of low dimensional, magnetic solids.

Toward inorganic electrides.

Electrides are materials in which alkali metals (Li through Cs) ionize to form bound alkali cations and "excess" electrons. The electrons reside in large cavities or channels or both in the host lattice. We report here the first synthesis of thermally stable inorganic electrides with cation-to-electron ratios of 1:1 as in organic electrides. Although alkali metal adducts to alumino-silicate zeolites are well known, the cation-to-electron ratio is generally 3:1 or greater because these zeolites contain alkali cations prior to incorporation of the alkali metal. In this work, two pure silica zeolites, ITQ-4and ITQ-7, with pore diameters of approximately 7 A, absorb up to 40 wt % cesium from the vapor phase (even at room temperature). The other alkali metals (except Li) can also be introduced at elevated temperatures. The optical and magnetic properties of the cesium-loaded samples suggest ionization to form Cs+ and e- with substantial electron-spin pairing. The metal-loaded samples are stable to at least 100 degrees C and are able to reduce small aromatic molecules such as benzene and naphthalene to the radical anions within the pores of the zeolite.

Structure and Properties of a New Electride, Rb+(cryptand[2.2.2])e.

This is the sixth electride whose crystal structure has been determined and the fourth to show polymorphism. Crystals of the title electride prepared from mixed solvents have a structure similar to that of Li+(cryptand[2.1.1])e-. Electrons occupy cavities that are connected by "ladder-like" channels. The static and spin magnetic susceptibilities of polycrystalline samples that contain this polymorph (called phase α) show Heisenberg 1D antiferromagnetic behavior with -J/kB = 30 K. Similar to other electrides with "localized" electrons, this electride is a poor conductor (σ < 10- 4 ohm-1cm-1). Thin films prepared by high vacuum co-deposition of Rb metal and cryptand[2.2.2] have optical spectra and near-metallic electrical conductivity nearly identical with those of K+(cryptand[2.2.2])e-. These properties would not be expected if the film structure were the same as that obtained for crystals. Rather, they suggest that the films consist of microcrystals whose structure is similar to that of K+(cryptand[2.2.2])e-. Polycrystalline samples prepared by slow evaporation of methylamine from stoichiometric solutions at -78 °C (called phase ß) have properties similar to those of K+(cryptand[2.2.2])e-. The conductivity of samples that contain phase ß is more than an order of magnitude larger than those with phase α. Magnetic and spin susceptibilities show that phase ß samples have much larger electron-electron interactions. As with K+(cryptand[2.2.2])e-, the magnetic susceptibility of phase ß is compatible with alternating linear chain Heisenberg antiferromagnetism, with -J/kB ≈ 300 K and -J'/kB ≈ 240 K. Thin vapor co-deposited films show abrupt changes in the conductivity and optical spectrum at -12 °C that suggest a transition that may be conversion of phase ß to phase α.

Aryl Oxalate Derivatives as Convenient Precursors for Generation of Aryloxyl Radicals.

The use of aryloxy oxalyl chlorides (AOCs), aryloxy oxalyl tert-butyl peroxides (AOBs), and diaryl oxalates (DAOs) for unimolecular generation of phenoxyl-based radicals under solution and rigid matrix conditions is described. AOCs are usable for photochemical generation of phenoxyl radicals, but are only conveniently stable as precursors when 2,6-di-tert-butylated derivatives are used. AOBs may be used as thermal precursors to aryloxyl radicals, since they typically decompose within 2-3 h at 60-85 degrees C to give phenols. (1)H-NMR solution kinetic studies find that DeltaH() = 31 kcal/mol, and DeltaS() = +3.4 cal/mol-K for decomposition of phenoxyoxalyl tert-butyl peroxide, consistent with substantial concertedness in peroxide bond cleavage. AOBs and the more stable DAOs are also convenient photochemical phenoxyl radical precursors. AOBs yield phenoxyl radicals more readily by photolysis than do corresponding DAOs, but the DAOs have fewer side reactions that can quench the product phenoxyl radicals.