Fabrication of Isolated Iron Nanowires.

Nanoscale interconnects are an important component of molecular electronics. Here we use X-ray spectromicroscopy techniques as well as scanning probe methods to explore the self-assembled growth of insulated iron nanowires as a potential means of supplying an earth abundant solution. The intrinsic anisotropy of a TiO2(110) substrate directs the growth of micron length iron wires at elevated temperatures, with a strong metal-support interaction giving rise to ilmenite (FeTiO3) encapsulation. Iron nanoparticles that decorate the nanowires display magnetic properties that suggest other possible applications.

Gold(i) bridged dimeric and trimeric heterometallic {Cr7Ni}-based qubit systems and their characterization.

Gold(i) bridged dimeric and trimeric structures of a ground state spin S = 1/2 heterometallic {Cr7Ni} wheel have been prepared and studied by continuous wave (CW) and pulsed wave EPR spectrometry. The {Cr7Ni} relaxation time constants (T1 and Tm) show rates matching well with previous observations. Four pulse Double Electron Resonance (DEER) studies suggest presence of more than one conformations. Small Angle X-ray Scattering (SAXS) in conjunction with Molecular Dynamic (MD) Simulations were performed to look at the possible conformations in solution. In line with DEER results, simulation data further indicated more flexible molecular geometry in solution than the one in solid state.

Self-assembly of a layered two-dimensional molecularly woven fabric.

Fabrics-materials consisting of layers of woven fibres-are some of the most important materials in everyday life1. Previous nanoscale weaves2-16 include isotropic crystalline covalent organic frameworks12-14 that feature rigid helical strands interlaced in all three dimensions, rather than the two-dimensional17,18 layers of flexible woven strands that give conventional textiles their characteristic flexibility, thinness, anisotropic strength and porosity. A supramolecular two-dimensional kagome weave15 and a single-layer, surface-supported, interwoven two-dimensional polymer16 have also been reported. The direct, bottom-up assembly of molecular building blocks into linear organic polymer chains woven in two dimensions has been proposed on a number of occasions19-23, but has not previously been achieved. Here we demonstrate that by using an anion and metal ion template, woven molecular 'tiles' can be tessellated into a material consisting of alternating aliphatic and aromatic segmented polymer strands, interwoven within discrete layers. Connections between slowly precipitating pre-woven grids, followed by the removal of the ion template, result in a wholly organic molecular material that forms as stacks and clusters of thin sheets-each sheet up to hundreds of micrometres long and wide but only about four nanometres thick-in which warp and weft single-chain polymer strands remain associated through periodic mechanical entanglements within each sheet. Atomic force microscopy and scanning electron microscopy show clusters and, occasionally, isolated individual sheets that, following demetallation, have slid apart from others with which they were stacked during the tessellation and polymerization process. The layered two-dimensional molecularly woven material has long-range order, is birefringent, is twice as stiff as the constituent linear polymer, and delaminates and tears along well-defined lines in the manner of a macroscopic textile. When incorporated into a polymer-supported membrane, it acts as a net, slowing the passage of large ions while letting smaller ions through.

Photoemission core level binding energies from multiple sized nanoparticles on the same support: TiO2(110)/Au.

A novel method of measuring the core level binding energies of multiple sized nanoparticles on the same substrate is demonstrated using the early stage of Au nanoparticle growth on reduced r-TiO2(110). This method employed in situ scanning tunneling microscopy (STM) and microfocused X-ray photoemission spectroscopy. An STM tip-shadowing method was used to synthesize patterned areas of Au nanoparticles on the substrate with different coverages and sizes. Patterns were identified and imaged using a UV photoelectron emission microscope. The Au 4f core level binding energies of the nanoparticles were investigated as a function of Au nanoparticle coverage and size. A combination of initial and final state effects modifies the binding energies of the Au 4f core levels as the nanoparticle size changes. When single Au atoms and Au3 clusters are present, the Au 4f7/2 binding energy, 84.42 eV, is similar to that observed at a high coverage (1.8 monolayer equivalent), resulting from a cancellation of initial and final state effects. As the coverage is increased, there is a decrease in binding energy, which then increases at a higher coverage to 84.39 eV. These results are consistent with a Volmer-Weber nucleation-growth model of Au nanoparticles at oxygen vacancies, resulting in electron transfer to the nanoparticles.

A [13]rotaxane assembled via a palladium molecular capsule.

Molecules that are the size of small proteins are difficult to make. The most frequently examined route is via self-assembly, and one particular approach involves molecular nanocapsules, where ligands are designed that will enforce the formation of specific polyhedra of metals within the core of the structure. Here we show that this approach can be combined with mechanically interlocking molecules to produce nanocapsules that are decorated on their exterior. This could be a general route to very large molecules, and is exemplified here by the synthesis and structural characterization of a [13]rotaxane, containing 150 metal centres. Small angle X-ray scattering combined with atomistic molecular dynamics simulations demonstrate the compound is intact in solution.

Formation of an interlocked double-chain from an organic-inorganic [2]rotaxane.

Here we show that a structure containing a polymeric interlocking daisy chain is obtained from the reaction of an inorganic-organic [2]rotaxane [HB{CrIII7NiII(µ-F)8(O2CtBu)16}], where B is an organic thread terminated with a bi-pyridyl unit, with an oxo-centered metal carboxylate triangle [FeIII2CoII(µ3-O)(O2CtBu)6(HO2CtBu)3].

Visualization of Water-Induced Surface Segregation of Polarons on Rutile TiO2(110).

Water-oxide surfaces are ubiquitous in nature and of widespread importance to phenomena like corrosion as well as contemporary industrial challenges such as energy production through water splitting. So far, a reasonably robust understanding of the structure of such interfaces under certain conditions has been obtained. Considerably less is known about how overlayer water modifies the inherent reactivity of oxide surfaces. Here we address this issue experimentally for rutile TiO2(110) using scanning tunneling microscopy and photoemission, with complementary density functional theory calculations. Through detailed studies of adsorbed water nanoclusters and continuous water overlayers, we determine that excess electrons in TiO2 are attracted to the top surface layer by water molecules. Measurements on methanol show similar behavior. Our results suggest that adsorbate-induced surface segregation of polarons could be a general phenomenon for technologically relevant oxide materials, with consequences for surface chemistry and the associated catalytic activity.

Author Correction: How to probe the spin contribution to momentum relaxation in topological insulators.

The original version of this Article contained an error in the spelling of the author Benjamin H. Williams, which was incorrectly given as Benjamin H. Willams. This has now been corrected in both the PDF and HTML versions of the Article.

How to probe the spin contribution to momentum relaxation in topological insulators.

Topological insulators exhibit a metallic surface state in which the directions of the carriers' momentum and spin are locked together. This characteristic property, which lies at the heart of proposed applications of topological insulators, protects carriers in the surface state from back-scattering unless the scattering centres are time-reversal symmetry breaking (i.e. magnetic). Here, we introduce a method of probing the effect of magnetic scattering by decorating the surface of topological insulators with molecules, whose magnetic degrees of freedom can be engineered independently of their electrostatic structure. We show that this approach allows us to separate the effects of magnetic and non-magnetic scattering in the perturbative limit. We thereby confirm that the low-temperature conductivity of SmB6 is dominated by a surface state and that the momentum of quasiparticles in this state is particularly sensitive to magnetic scatterers, as expected in a topological insulator.

An Extensive Family of Heterometallic Titanium(IV)-Metal(III) Rings with Structure Control through Templates.

A family of heterometallic [Cat][Tix MO(x+1 )(O2 Ct Bu)2x+2 ] rings is reported where Cat=a secondary or tertiary alkyl ammonium ion, x=7, 8 or 9, and M=FeIII , GaIII , CrIII , InIII and AlIII . The structures are regular polygons with eight, nine or ten vertices with each edge bridged by an oxide and two pivalates. The size of the ring formed is controlled by the alkylammonium cation present. In each case a homometallic by-product is found [Cat][Tix O(x+1 )(O2 Ct Bu)2x-1 ].

Use of Supramolecular Assemblies as Lithographic Resists.

A new resist material for electron beam lithography has been created that is based on a supramolecular assembly. Initial studies revealed that with this supramolecular approach, high-resolution structures can be written that show unprecedented selectivity when exposed to etching conditions involving plasmas.

Nanostructured Aptamer-Functionalized Black Phosphorus Sensing Platform for Label-Free Detection of Myoglobin, a Cardiovascular Disease Biomarker.

We report the electrochemical detection of the redox active cardiac biomarker myoglobin (Mb) using aptamer-functionalized black phosphorus nanostructured electrodes by measuring direct electron transfer. The as-synthesized few-layer black phosphorus nanosheets have been functionalized with poly-l-lysine (PLL) to facilitate binding with generated anti-Mb DNA aptamers on nanostructured electrodes. This aptasensor platform has a record-low detection limit (∼0.524 pg mL(-1)) and sensitivity (36 µA pg(-1) mL cm(-2)) toward Mb with a dynamic response range from 1 pg mL(-1) to 16 µg mL(-1) for Mb in serum samples. This strategy opens up avenues to bedside technologies for multiplexed diagnosis of cardiovascular diseases in complex human samples.

Making hybrid [n]-rotaxanes as supramolecular arrays of molecular electron spin qubits.

Quantum information processing (QIP) would require that the individual units involved--qubits--communicate to other qubits while retaining their identity. In many ways this resembles the way supramolecular chemistry brings together individual molecules into interlocked structures, where the assembly has one identity but where the individual components are still recognizable. Here a fully modular supramolecular strategy has been to link hybrid organic-inorganic [2]- and [3]-rotaxanes into still larger [4]-, [5]- and [7]-rotaxanes. The ring components are heterometallic octanuclear [Cr7NiF8(O2C(t)Bu)16](-) coordination cages and the thread components template the formation of the ring about the organic axle, and are further functionalized to act as a ligand, which leads to large supramolecular arrays of these heterometallic rings. As the rings have been proposed as qubits for QIP, the strategy provides a possible route towards scalable molecular electron spin devices for QIP. Double electron-electron resonance experiments demonstrate inter-qubit interactions suitable for mediating two-qubit quantum logic gates.

g-Engineering in Hybrid Rotaxanes To Create AB and AB2 Electron Spin Systems: EPR Spectroscopic Studies of Weak Interactions between Dissimilar Electron Spin Qubits.

Hybrid [2]rotaxanes and pseudorotaxanes are reported where the magnetic interaction between dissimilar spins is controlled to create AB and AB2 electron spin systems, allowing independent control of weakly interacting S=${{ 1/2 }}$ centers.

Influence of support morphology on the bonding of molecules to nanoparticles.

Supported metal nanoparticles form the basis of heterogeneous catalysts. Above a certain nanoparticle size, it is generally assumed that adsorbates bond in an identical fashion as on a semiinfinite crystal. This assumption has allowed the database on metal single crystals accumulated over the past 40 years to be used to model heterogeneous catalysts. Using a surface science approach to CO adsorption on supported Pd nanoparticles, we show that this assumption may be flawed. Near-edge X-ray absorption fine structure measurements, isolated to one nanoparticle, show that CO bonds upright on the nanoparticle top facets as expected from single-crystal data. However, the CO lateral registry differs from the single crystal. Our calculations indicate that this is caused by the strain on the nanoparticle, induced by carpet growth across the substrate step edges. This strain also weakens the CO-metal bond, which will reduce the energy barrier for catalytic reactions, including CO oxidation.

Controlled Synthesis of Nanoscopic Metal Cages.

Here we show an elegant and general route to the assembly of a giant {M12C24} cage from 12 palladium ions (M) and 24 heterometallic octanuclear coordination cages (C = {Cr7Ni-Py2}). The molecule is 8 nm in size, and the methods for its synthesis and characterization provide a basis for future developments at this scale.

Electrochemistry of well-defined graphene samples: role of contaminants.

We report the electrochemical characterisation of well-defined graphene samples, prepared by mechanical exfoliation. Mechanical exfoliation is the method of choice for high purity graphene samples, despite the inherent complexity of the approach and the small scale of the resultant flakes. However, one important, yet presently unclear area, is the role of adsorbates such as processing residue, on the properties of the graphene layer. We report high resolution microscopic and electrochemical characterisation of a variety of poly(methyl methacrylate) (PMMA) transferred graphene samples, with the explicit aim of investigating the relationship between electrochemical activity and sample purity.

Lanthanide template synthesis of a molecular trefoil knot.

We report on a complex featuring three 2,6-pyridinedicarboxamide ligands entwined around a lanthanide (Ln(3+)) ion. The ligand strands can be cyclized by ring-closing olefin metathesis to form a molecular trefoil knot in 58% yield. Demetalation with tetraethylammonium fluoride quantitatively generates the wholly organic 81-atom-loop trefoil knot.

CO and O overlayers on Pd nanocrystals supported on TiO2(110).

We have prepared a model catalytic system by depositing Pd onto a TiO2(110) surface held at approximately 720 K. Scanning tunneling microscopy (STM) reveals well-defined Pd nanocrystals consisting of (111) top facets with {111} and {100} side facets. The Pd nanocrystals go down to about 10 nm in width and 1.3 nm in height. Top facets can be imaged with atomic resolution, indicating the absence of TiOx encapsulation. The model catalyst was probed by exposure to CO and O2. By varying the CO exposure, different CO overlayers were formed on the (111) top facets, with coverages ranging from 0.33 to 0.75 of a monolayer. Near edge X-ray absorption fine structure (NEXAFS) measurements at 300 K reveal that at around 0.5 ML coverage, CO is oriented with the molecular axis more or less normal to TiO2(110). Dosing small amounts of 02 separately on a Pd/ TiO2(110) surface led to an overlayer of p(2 x 2)-O formed on the (111) top facet of the Pd nanocrystals at 190 K.

Rings and threads as linkers in metal-organic frameworks and poly-rotaxanes.

Coordination polymers and metal-organic rotaxane frameworks are reported where the organic linker is replaced by functionalised inorganic clusters that act as bridging ligands.