An electrically conducting 3D coronene-based metal-organic framework.

A novel cubic mesoporous metal-organic framework (MOF), consisting of hexahydroxy-cata-hexabenzocoronene (c-HBC) and FeIII ions is presented. The highly crystalline and porous MOF features broad optical absorption over the whole visible and near infrared spectral regions. An electrical conductivity of 10-4 S cm-1 was measured on a pressed pellet.

Transpassive Metal Dissolution vs. Oxygen Evolution Reaction: Implication for Alloy Stability and Electrocatalysis.

Multi-principal element alloys (MPEAs) are gaining interest in corrosion and electrocatalysis research due to their electrochemical stability across a broad pH range and the design flexibility they offer. Using the equimolar CrCoNi alloy, we observe significant metal dissolution in a corrosive electrolyte (0.1 M NaCl, pH 2) concurrently with the oxygen evolution reaction (OER) in the transpassive region, despite the absence of hysteresis in polarization curves or other obvious corrosion indicators. We present a characterization scheme to delineate the contribution of OER and alloy dissolution, using scanning electrochemical microscopy (SECM) for OER-onset detection, and quantitative chemical analysis with inductively coupled-mass spectrometry (ICP-MS) and ultraviolet visible light (UV/Vis) spectrometry to elucidate metal dissolution processes. In situ electrochemical atomic force microscopy (EC-AFM) revealed that the transpassive metal dissolution on CrCoNi is dominated by intergranular corrosion. These results have significant implications for the stability of MPEAs in corrosion systems, emphasizing the necessity of analytically determining metal ions released from MPEA electrodes into the electrolyte when evaluating Faradaic efficiencies of OER catalysts. The release of transition metal ions not only reduces the Faradaic efficiency of electrolyzers but may also cause poisoning and degradation of membranes in electrochemical reactors.

Unidirectional Current in Layered Metal Hexacyanometallate Thin Films: Implication for Alternative Wet-Processed Electronic Materials.

Rectifying behavior of alternative electronic materials is demonstrated with layered structures of a crystalline coordination network whose mixed ionic and electronic conductivity can be manipulated by switching the redox state of coordinated transition-metal ions. The coordinated transition-metal ions can convey additional functionality such as (redox)catalysis or electrochromism. In order to obtain rectifying behavior and charge trapping, layered films of such materials are explored. Specifically, layered films of iron hexacyanoruthenate (Fe-HCR) and nickel hexacyanoferrate (Ni-HCF) were formed by the combination of different deposition procedures. They comprise electrodeposition during voltammetric cycles for Fe-HCR and Ni-HCF, layer-by-layer deposition of Ni-HCF without redox chemistry, and drop casting of presynthesized Ni-HCF nanoparticles. The obtained materials were structurally characterized by X-ray diffraction analysis, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy for nanoparticles, and scanning force microscopy (SFM). Voltammetry in 1 mol L-1 KCl and current-voltage curves (I-V curves) recorded between a conductive SFM tip and the back electrode outside of an electrolyte solution demonstrated charge trapping and rectifying behavior based on the different formal potentials of the redox centers in the films.

Nanoporous Gold: From Structure Evolution to Functional Properties in Catalysis and Electrochemistry.

Nanoporous gold (NPG) is characterized by a bicontinuous network of nanometer-sized metallic struts and interconnected pores formed spontaneously by oxidative dissolution of the less noble element from gold alloys. The resulting material exhibits decent catalytic activity for low-temperature, aerobic total as well as partial oxidation reactions, the oxidative coupling of methanol to methyl formate being the prototypical example. This review not only provides a critical discussion of ways to tune the morphology and composition of this material and its implication for catalysis and electrocatalysis, but will also exemplarily review the current mechanistic understanding of the partial oxidation of methanol using information from quantum chemical studies, model studies on single-crystal surfaces, gas phase catalysis, aerobic liquid phase oxidation, and electrocatalysis. In this respect, a particular focus will be on mechanistic aspects not well understood, yet. Apart from the mechanistic aspects of catalysis, best practice examples with respect to material preparation and characterization will be discussed. These can improve the reproducibility of the materials property such as the catalytic activity and selectivity as well as the scope of reactions being identified as the main challenges for a broader application of NPG in target-oriented organic synthesis.

Dry Synthesis of Pure and Ultrathin Nanoporous Metallic Films.

Nanoporous metals possess unique properties attributed to their high surface area and interconnected nanoscale ligaments. They are mostly fabricated by wet synthetic methods that are not universal to various metals and not free from impurities due to solution-based etching processes. Here, we demonstrate that the plasma treatment of metal nanoparticles formed by physical vapor deposition is a general route to form such films with many metals including the non-noble ones. The resultant nanoporous metallic films are free of impurities and possess highly curved ligaments and nanopores. The metal films are ultrathin, yet remarkably robust and very well connected, and thus are highly promising for various applications such as transparent conducting electrodes.

Combinatorial Screening of Cu-W Oxide-Based Photoanodes for Photoelectrochemical Water Splitting.

Metal oxide libraries for photoanodes for the oxygen evolution reaction (OER) were generated by printing a metal salt solution in an array layout, followed by calcination to yield 22 ternary metal oxide systems. The libraries included a ternary metal cation system based on CuWO4 with one out of eight transition or posttransition metal ions Cr, Mn, Fe, Co, Ni, Zn, Bi, and Ga in different overall atomic ratios. The photocatalyst libraries were screened by scanning photoelectrochemical microscopy for the highest anodic photocurrents. Array elements that showed promising performance were printed in another set of eight libraries with smaller increments of overall composition. Improved performance with respect to CuWO4 was found for Ga, Co, and Ni as the third element. A comparison of the most active composition of those arrays within one library showed the highest activity for Cu48Ga3W49Ox. Printing spots of identical composition (Cu48Ga3W49Ox, Cu44Ni9W47Ox, and Cu44Co9W47Ox) over a larger area facilitated further characterization by X-ray photoelectron spectroscopy ultraviolet photoelectron spectroscopy (UPS), X-ray diffraction, scanning electron microscopy, chopped light voltammetry, and scanning electrochemical microscopy for the OER. High and stable steady-state photocurrents were generated in a photoelectrochemical cell for all three electrodes even at a low constant bias voltage. The best overall photoanode composition Cu48Ga3W49Ox showed currents that were 36 times higher than the currents of the binary Cu50W50Ox system. Significant n-doping was found by UPS valence band spectra for Ga-containing materials.

Effect of a Cocatalyst on a Photoanode in Water Splitting: A Study of Scanning Electrochemical Microscopy.

With a proper band gap of ∼2.4 eV for solar light absorption and suitable valence band edge position for oxygen evolution, scheelite-monoclinic bismuth vanadate (BiVO4) has become one of the most attractive photocatalysts for efficient visible-light-driven photoelectrochemical (PEC) water splitting. Several studies have indicated that surface modification of BiVO4 with a cocatalyst such as NiFe layered double hydroxide (LDH) can significantly increase the PEC water splitting performance of the catalyst. Herein, we experimentally investigated the charge transfer dynamics and charge carrier recombination processes by scanning electrochemical microscopy (SECM) with the feedback mode on the surface of BiVO4 and BiVO4/NiFe-LDH as model samples. The ratio of rate constants for photogenerated hole (kh+0) to electron (ke-0) via the photocatalyst of BiVO4/NiFe-LDH reacting with the redox couple is found to be five times larger than that of BiVO4 under illumination. In this case, the ratio of the rate constants kh+0/ke-0 stands for the interfacial charge recombination process. This implies the cocatalyst NiFe-LDH suppresses the electron back transfer greatly and finally reduces the surface recombination. Control experiments with cocatalysts CoPi and RuOx onto BiVO4 further verify this conclusion. Therefore, the SECM characterization allows us to make an overall analysis on the function of cocatalysts in the PEC water splitting system.

An Electrically Conducting Three-Dimensional Iron-Catecholate Porous Framework.

We report the synthesis of a unique cubic metal-organic framework (MOF), Fe-HHTP-MOF, comprising hexahydroxytriphenylene (HHTP) supertetrahedral units and FeIII ions, arranged in a diamond topology. The MOF is synthesized under solvothermal conditions, yielding a highly crystalline, deep black powder, with crystallites of 300-500 nm size and tetrahedral morphology. Nitrogen sorption analysis indicates a highly porous material with a surface area exceeding 1400 m2 g-1 . Furthermore, Fe-HHTP-MOF shows broadband absorption from 475 up to 1900 nm with excellent absorption capability of 98.5 % of the incoming light over the visible spectral region. Electrical conductivity measurements of pressed pellets reveal a high intrinsic electrical conductivity of up to 10-3  S cm-1 . Quantum mechanical calculations predict Fe-HHTP-MOF to be an efficient electron conductor, exhibiting continuous charge-carrier pathways throughout the structure.

Impact of the Crystalline Li15Si4 Phase on the Self-Discharge Mechanism of Silicon Negative Electrodes in Organic Electrolytes.

Because of their high specific capacity and rather low operating potential, silicon-based negative electrode materials for lithium-ion batteries have been the subject of extensive research over the past 2 decades. Although the understanding of the (de)lithiation behavior of silicon has significantly increased, several major challenges have not been solved yet, hindering its broad commercial application. One major issue is the low initial Coulombic efficiency and the ever-present self-discharge of silicon electrodes. Self-discharge itself affects the long-term stability of electrochemical storage systems and, additionally, must be taken into consideration for inevitable prelithiation approaches. The impact of the crystalline Li15Si4 phase is of great interest as the phase transformation between crystalline (c) and amorphous (a) phases not only increases the specific surface area but also causes huge polarization. Moreover, there is the possibility for electrochemical over-lithiation toward the Li15+aSi4 phase because of the electron-deficient Li15Si4 phase, which can be highly reactive toward the electrolyte. This poses the question about the impact of the c-Li15Si4 phase on the self-discharge behavior in comparison to its amorphous counterpart. Here, silicon thin films used as model electrodes are lithiated to cut-off potentials of 10 mV and 50 mV versus Li|Li+ (U10mV and U50mV) in order to systematically investigate their self-discharge mechanism via open-circuit potential (UOCP) measurements and to visualize the solid electrolyte interphase (SEI) growth by means of scanning electrochemical microscopy. We show that the c-Li15Si4 phase is formed for the U10mV electrode, while it is not found for the U50mV electrode. In turn, the U50mV electrode displays an almost linear self-discharge behavior, whereas the U10mV electrode reaches a UOCP plateau at ca. 380 mV versus Li|Li+, which is due to the phase transition from c-Li15Si4 to the a-LixSi phase. At this plateau potential, the phase transformation at the Si|electrolyte interface results in an electronically more insulating and more uniform SEI (U10mV electrode), while the U50mV electrode displays a less uniform SEI layer. In summary, the self-discharge mechanism of silicon electrodes and, hence, the irreversible decomposition of the electrolyte and the corresponding SEI formation process heavily depend on the structural nature of the underlying lithium-silicon phase.

Electrochemical Activation of Self-Assembled Monolayers for the Binding of Effectors.

A self-assembled monolayer (SAM) on gold was prepared from a diaminoterephthalate (DAT) derivative as functional molecule and 1-decanthiol as a backfiller. The DAT derivative is N-protected by a tert-butyloxycarbonyl (Boc) group and is anchored to the gold surface via a liponic acid as a stable anchor group. The terminal DAT moiety exhibits interesting effector properties such as fluorescence and electrochemical activity. Irreversible oxidation of the monolayer at 0.4 V (Hg|Hg2SO4) in 0.1 M HClO4 triggers deprotection of the DAT group and subsequent chemical reactions, during which 10% of the DAT groups of the original SAM are transformed to a new surface-bound, quasi-reversible redox couple with a formal potential of 0.0 V (Hg|Hg2SO4) and a standard rate constant of 8 s-1 in 0.1 M HClO4. Immersion of the mixed SAM in 0.1 M HClO4 at open circuit potential or oxidation in 0.1 M H2SO4 did not produce this surface-bound redox couple. The monolayers were thoroughly characterized by X-ray photoelectron spectroscopy (XPS) and polarization modulation infrared reflection absorption spectroscopy (PM IRRAS) after the different preparation steps indicating only minor changes in the overall composition of the monolayer, in particular, the preservation of the heteroatoms. The new redox couple is likely a diimine, in agreement with its ability to bind nucleophiles such as anilines by conjugate addition that could be followed by multicycle voltammetry and XPS. The DAT effector group is especially interesting because it can also report the binding reaction by changed electrochemical and fluorescence signals.

Electronic Transitions in Different Redox States of Trinuclear 5,6,11,12,17,18-Hexaazatrinaphthylene-Bridged Titanium Complexes: Spectroelectrochemistry and Quantum Chemistry.

Multinuclear transition metal complexes bridged by ligands with extended π-electronic systems show a variety of complex electronic transitions and electron transfer reactions. While a systematic understanding of the photochemistry and electrochemistry has been attained for binuclear complexes, much less is known about trinuclear complexes such as hexaphenyl-5,6,11,12,17,18-hexaazatrinaphthylene-tristitanocene [(Cp2 Ti)3 HATN(Ph)6 ]. The voltammogram of [(Cp2 Ti)3 HATN(Ph)6 ] shows six oxidation and three reduction waves. Solution spectra of [(Cp2 Ti)3 HATN(Ph)6 ] and of the electrochemically formed oxidation products show electronic transitions in the UV, visible and the NIR ranges. Density functional theory (DFT) and linear response time-dependent DFT show that the three formally titanium(II) centers transfer an electron to the HATN ligand in the ground state. The optically excited transitions occur exclusively between ligand-centered orbitals. The charged titanium centers only provide an electrostatic frame to the extended π-electronic system. Complete active self-consistent field (CASSCF) calculation on a structurally simplified model compound, which considers the multi-reference character imposed by the three titanium centers, can provide an interpretation of the experimentally observed temperature-dependent magnetic behavior of the different redox states of the title compound in full consistency with the interpretation of the electronic spectra.

Catalytic Activity of Alkali Metal Cations for the Chemical Oxygen Reduction Reaction in a Biphasic Liquid System Probed by Scanning Electrochemical Microscopy.

Chemical reduction of dioxygen in organic solvents for the production of reactive oxygen species or the concomitant oxidation of organic substrates can be enhanced by the separation of products and educts in biphasic liquid systems. Here, the coupled electron and ion transfer processes is studied as well as reagent fluxes across the liquid|liquid interface for the chemical reduction of dioxygen by decamethylferrocene (DMFc) in a dichloroethane-based organic electrolyte forming an interface with an aqueous electrolyte containing alkali metal ions. This interface is stabilized at the orifice of a pipette, across which a Galvani potential difference is externally applied and precisely adjusted to enforce the transfer of different alkali metal ions from the aqueous to the organic electrolyte. The oxygen reduction is followed by H2 O2 detection in the aqueous phase close to the interface by a microelectrode of a scanning electrochemical microscope (SECM). The results prove a strong catalytic effect of hydrated alkali metal ions on the formation rate of H2 O2 , which varies systematically with the acidity of the transferred alkali metal ions in the organic phase.

A highly crystalline anthracene-based MOF-74 series featuring electrical conductivity and luminescence.

Recently, a small group of metal-organic frameworks (MOFs) has been discovered featuring substantial charge transport properties and electrical conductivity, hence promising to broaden the scope of potential MOF applications in fields such as batteries, fuel cells and supercapacitors. In combination with light emission, electroactive MOFs are intriguing candidates for chemical sensing and optoelectronic applications. Here, we incorporated anthracene-based building blocks into the MOF-74 topology with five different divalent metal ions, that is, Zn2+, Mg2+, Ni2+, Co2+ and Mn2+, resulting in a series of highly crystalline MOFs, coined ANMOF-74(M). This series of MOFs features substantial photoluminescence, with ANMOF-74(Zn) emitting across the whole visible spectrum. The materials moreover combine this photoluminescence with high surface areas and electrical conductivity. Compared to the original MOF-74 materials constructed from 2,5-dihydroxy terephthalic acid and the same metal ions Zn2+, Mg2+, Ni2+, Co2+ and Mn2+, we observed a conductivity enhancement of up to six orders of magnitude. Our results point towards the importance of building block design and the careful choice of the embedded MOF topology for obtaining materials with desired properties such as photoluminescence and electrical conductivity.

Electron Transfer and Electron Excitation Processes in 2,5-Diaminoterephthalate Derivatives with Broad Scope for Functionalization.

Derivatives of 2,5-diaminoterephthalate (DAT) are efficient fluorescence dyes that are also redox-active, thus allowing for the electrochemical manipulation of spectral properties. The electrochemical behaviour of seven DAT derivatives was studied by cyclic voltammetry in dichloromethane. In the absence of a proton donor, DATs should be oxidized in two one-electron steps. The first step is usually quasi-reversible while the second step is either quasi-reversible or irreversible. Some electrochemical properties such as the formal potentials and the ratio between the anodic and the cathodic current were determined from the cyclic voltammograms. Correlation between the formal potential of first oxidation and the absorption or the fluorescence emission wavelengths are established for this specific type of dyes. These correlations were confirmed with density functional theory calculations.

Diverging surface reactions at TiO2- or ZnO-based photoanodes in dye-sensitized solar cells.

Fast recombination of electrons from semiconductors with the oxidized redox species in the electrolyte represents a major bottleneck in the improvement of ZnO-based dye-sensitized solar cells (DSSCs). While processes at the semiconductor-electrolyte interface are well studied on TiO2 electrodes, the interactions of the ZnO surface with the electrolyte solution in DSSCs are less explored. This work aims at clarifying the different impact of the two contrasting redox couples I3-/I- or [Co(bpy-pz)2]3+/2+ (bpy-pz = bis(6-(1H-pyrazol-1-yl)-2,2'-bipyridine)) in electrolytes containing either no additives or Li+ ions and/or 4-tert-butlypyridine (TBP) in DSSCs using screen-printed nanoparticulate TiO2 (NP-TiO2) or electrodeposited ZnO (ED-ZnO) photoanodes sensitized with the indoline dye DN216. A detailed photoelectrochemical study is performed to investigate light absorption, charge transfer and mass transport in these cells. We demonstrate that the chemical nature of the semiconductor directly influences the affinity of adsorbates. This drastically influences the energy levels and recombination kinetics at the semiconductor-electrolyte interface, electron and ion transport in the porous system as well as light absorption of dye molecules by the Stark effect. The present investigation reveals the origin of major performance losses in DSSCs based on ED-ZnO photoanodes as well as the relevance of ionic interactions with NP-TiO2 photoanodes that can both serve as the starting point for rationally guided improvement of their conversion efficiencies.

Diaminoterephthalate-α-lipoic acid conjugates with fluorinated residues.

Two bifunctional diaminoterephthalate (DAT) fluorescence dyes were prepared in a three-step sequence including one deprotection reaction. One functional unit is α-lipoic acid (ALA) for binding the dye to gold surfaces. It was introduced to the DAT scaffold by an amidation reaction. The other functional unit is a para-(trifluoromethyl)benzyl group for facile detection of the surface-bound material by X-ray photoelectron spectroscopy (XPS). This residue was introduced by reductive amination of the DAT scaffold with the respective benzaldehyde derivative. In one compound (60% yield over three steps) the ALA unit is directly bound to the DAT as a relatively electron-withdrawing amide. In solution (CH2Cl2), this material shows strong fluorescence (quantum yield 57% with emission at 495 nm, absorption maximum at 420 nm). The other compound (57% yield over three steps) possesses a propylene spacer between the ALA and the DAT units for electronic decoupling, thus, bathochromic shifts are observed (absorption at 514 nm, emission at 566 nm). The quantum yield is, however, lower (4%). Self-assembled monolayers on a gold surface of both compounds were prepared and characterized by high-resolution XPS of the C 1s, O 1s, S 2p, N 1s and F 1s emissions. The high signal-to-noise ratios of the F 1s peaks indicated that trifluoromethylation is an excellent tool for the detection of surface-bound materials by XPS.

Correlations of Crystal and Electronic Structure via NMR and X-ray Photoelectron Spectroscopies in the RETMAl2 (RE = Sc, Y, La-Nd, Sm, Gd-Tm, Lu; TM = Ni, Pd, Pt) Series.

A total of 35 intermetallic aluminum compounds have been synthesized from the elements via arc melting and characterized by powder X-ray diffraction. A total of 15 of them have been previously reported; however, detailed property investigations were missing. Compounds of the RETMAl2 (rare earth metal RE = Sc, Y, La-Nd, Sm, Gd-Tm, Lu) series with transition metal TM = Ni, Pd, and Pt crystallize isostructurally in the orthorhombic MgCuAl2 type structure ( Cmcm, oC16, fc2). Single-crystal X-ray diffraction investigations were conducted on YNiAl2, LaNiAl2, YPdAl2, ScPtAl2, and YPtAl2. The TM and Al atoms form a [TMAl2]δ- polyanion, the RE atoms reside in cavities within the framework. While the Sc, Y, La, and Lu compounds exhibit Pauli-paramagnetic behavior, consistent with all atoms being closed shell, the other RETMAl2 compounds show paramagnetism along with magnetic ordering at low temperatures, in line with an open-shell trivalent oxidation state for the RE atoms. Solid-state 27Al NMR investigations were carried out on the Pauli-paramagnetic samples, all showing only a single central transition, in line with one crystallographic site for the respective atoms. The observed quadrupolar coupling constants and electric-field-gradient asymmetry parameters were found to be in good agreement with the density-functional-theory-calculated values. Isotropic resonance shifts are dominated by the Fermi-contact interactions with s-conduction electron densities at the Fermi edge (Knight shifts). The bonding characteristics mirror the electronic density of states and crystal chemistry of the family of intermetallic compounds under consideration. Both the Knight shifts and quadrupolar coupling constants can be predicted based on element-specific increments.

Vectorial near-field coupling.

The coherent exchange of optical near fields between two neighbouring dipoles plays an essential role in the optical properties, quantum dynamics and thus the function of many naturally occurring and artificial nanosystems. These interactions are challenging to quantify experimentally. They extend over only a few nanometres and depend sensitively on the detuning, dephasing and relative orientation (that is, the vectorial properties) of the coupled dipoles. Here, we introduce plasmonic nanofocusing spectroscopy to record coherent light scattering spectra with 5 nm spatial resolution from the apex of a conical gold nanotaper. The apex is excited solely by evanescent fields and coupled to plasmon resonances in a single gold nanorod. We resolve resonance energy shifts and line broadenings as a function of dipole distance and relative orientation. We demonstrate how these phenomena arise from mode couplings between different vectorial components of the interacting optical near fields, specifically from the coupling of the nanorod to both transverse and longitudinal polarizabilities of the taper apex.

Synthesis, Crystal Structure, and Selected Properties of [Au(S2 CNH2 )2 ]SCN: A Precursor for Gold Macro-Needles Consisting of Gold Nanoparticles Glued by Graphitic Carbon Nitride.

A new preparation route is developed for the synthesis of needle-like crystals of [Au(S2 CNH2 )2 ]SCN, which avoids disproportionation of the AuI salt used as a starting material. In the crystal structure, the two crystallographically independent AuIII centers are in a square-planar environment of two S2 CNH2 ligands. The Hirshfeld surface analysis reveals the presence of noncovalent intermolecular S⋅⋅⋅S interactions, which are essential for the spatial arrangement of the molecules. Density functional theory (DFT) calculations including dispersion and damping corrections result in a unit cell volume very close to the value determined experimentally. Thermal decomposition in an inert atmosphere generates black needles with lengths of up to 500 µm. X-ray powder diffraction and pair distribution function analyses demonstrate that the needles are composed of nanosized crystals with a volume-weighted average domain size of 20(1) nm. According to results of X-ray photoemission experiments, the black needles are covered by a nitrogen-rich carbon nitride with composition near (CN)2 N. 13 C solid-state NMR investigations indicate that two different carbon species are present, with signals corresponding well to heptazine units as in melon and triazine units as in poly(triazin imide) type compounds. Scanning transmission electron microscopy tomography evidences that the needles are composed of slightly elongated nanoparticles.

Printing with Satellite Droplets.

Despite their specific methodologies, all current noncontact printing techniques such as inkjet printing (IJP), involve the break-up of a liquid meniscus during the separation of the ink droplet from the bulk ink reservoir. Often, the break-up of a liquid meniscus results in the formation of one or more satellite droplet whose volumes are several orders of magnitude smaller than the primary droplet. Many attempts are directed to suppress or control the formation of satellite droplets because they blur the printing result. For the first time, a simple mechanism by which a single satellite droplet is exclusively formed and directed to the substrate by a gas stream while the primary droplet remains attached to a metal rod used for controlling the formation and break-up of the meniscus is reported. High printing resolution is demonstrated by satellite droplets printing (SDP) without the need for small orifices which are prone to clogging. Furthermore, the droplet generation from a large orifice enables SDP to handle viscous inks which has remained challenging for traditional IJP.