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Heteroatom substitution into the cores of alternant, aromatic hydrocarbons containing only even-membered rings is attracting increasing interest as a method of tuning their electrical conductance. Here, the effect of heteroatom substitution into molecular cores of non-alternant hydrocarbons, containing odd-membered rings, is examined. Benzodichalcogenophene (BDC) compounds are rigid, planar π-conjugated structures, with molecular cores containing five-membered rings fused to a six-membered aryl ring. To probe the sensitivity or resilience of constructive quantum interference (CQI) in these non-bipartite molecular cores, two C2-symmetric molecules (I and II) and one asymmetric molecule (III) were investigated. I (II) contains S (O) heteroatoms in each of the five-membered rings, while III contains an S in one five-membered ring and an O in the other. Differences in their conductances arise primarily from the longer S−C and shorter O−C bond lengths compared with the C−C bond and the associated changes in their resonance integrals. Although the conductance of III is significantly lower than the conductances of the others, CQI was found to be resilient and persist in all molecules.  相似文献   

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Constructing single‐molecule parallel circuits with multiple conduction channels is an effective strategy to improve the conductance of a single molecular junction, but rarely reported. We present a novel through‐space conjugated single‐molecule parallel circuit (f‐4Ph‐4SMe) comprised of a pair of closely parallelly aligned p‐quaterphenyl chains tethered by a vinyl bridge and end‐capped with four SMe anchoring groups. Scanning‐tunneling‐microscopy‐based break junction (STM‐BJ) and transmission calculations demonstrate that f‐4Ph‐4SMe holds multiple conductance states owing to different contact configurations. When four SMe groups are in contact with two electrodes at the same time, the through‐bond and through‐space conduction channels work synergistically, resulting in a conductance much larger than those of analogous molecules with two SMe groups or the sum of two p‐quaterphenyl chains. The system is an ideal model for understanding electron transport through parallel π‐stacked molecular systems and may serve as a key component for integrated molecular circuits with controllable conductance.  相似文献   

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The adsorption geometry and the electronic structure of a Blatter radical derivative on a gold surface were investigated by a combination of high‐resolution noncontact atomic force microscopy and scanning tunneling microscopy. While the hybridization with the substrate hinders direct access to the molecular states, we show that the unpaired‐electron orbital can be probed with Ångström resolution by mapping the spatial distribution of the Kondo resonance. The Blatter derivative features a peculiar delocalization of the unpaired‐electron orbital over some but not all moieties of the molecule, such that the Kondo signature can be related to the spatial fingerprint of the orbital. We observe a direct correspondence between these two quantities, including a pronounced nodal plane structure. Finally, we demonstrate that the spatial signature of the Kondo resonance also persists upon noncovalent dimerization of molecules.  相似文献   

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Reported here is a molecular dipole that self‐assembles into highly ordered patterns at the liquid‐solid interface, and it can be switched at room temperature between a bright and a dark state at the single‐molecule level. Using a scanning tunneling microscope (STM) under suitable bias conditions, binary information can be written at a density of up to 41 Tb cm?2 (256 Tb/in2). The written information is stable during reading at room temperature, but it can also be erased at will, instantly, by proper choice of tunneling conditions. DFT calculations indicate that the contrast and switching mechanism originate from the stacking sequence of the molecular dipole, which is reoriented by the electric field between the tip and substrate.  相似文献   

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Scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) were performed on monolayer film of NiTPP supported on Au(111) under ultrahigh vacuum (UHV) conditions. The constant current STM images show remarkable bias dependence. High resolution STM data clearly show the individual NiTPP molecules and allow easy differentiation between NiTPP and CoTPP reported before. Scanning tunneling spectra, as a function of molecule-tip separation, were acquired over a range of tip motion of 0.42 nm. Spectra do not show the variation in band splitting with tip distance. It appears for molecules such as NiTPP that the average potential at the molecule is essentially the same at the same metal substrate. For molecules of the height of NiTPP, the scanning tunneling spectra should give reliable occupied and unoccupied orbital energies over a wide range of tip-molecule distances.  相似文献   

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Basic regularities of electrochemical processes in the gap of an ex situ scanning tunneling microscope in conditions of condensation of air moisture at the sample surface are considered on a qualitative level. A layer of condensed moisture is viewed as an electrolyte in a two-electrode cell. The depolarizers present in this layer may experience electrochemical conversions on the tip and in an area of the sample surface near the tip. As a result, the recorded “tunneling” current includes electrochemical constituents. Depending on the electrochemical processes in the gap, various dependences of the tip-sample distance on the current and applied voltage can be expected. For preliminary diagnostics of processes in the gap it is suggested to use voltage-height spectra, whose shape and characteristic heights are sensitive to the nature and location of redox active species. Experimental data for various films on conducting supports (quasi-two-dimensional adsorbed layers of hemin and peroxidase, electrodeposited nonstoichiometric tungsten oxides, doped tin dioxide, solid electrolyte with ionic conduction) are presented as an examples.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 583–595.Original Russian Text Copyright © 2005 by Yusipovich, Vassiliev.  相似文献   

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We report the on-surface synthesis and spectroscopic study of laterally extended chevron graphene nanoribbons (GNRs) and compare them with the established chevron GNRs, emphasizing the consistency of bandgap reduction of semiconducting GNRs with increased width. The laterally extended chevron GNRs grown on Au(111) exhibit a bandgap of about 2.2 eV, which is considerably smaller than the values reported for chevron GNRs in similar studies.  相似文献   

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We have studied the growth of Ag on Si(5 5 12) using scanning tunneling microscopy and spectroscopy (STM/STS). At metal coverages as low as 0.05 monolayer (ML), Ag forms well-ordered overlayer rows, or one-dimensional clusters, on the underlying silicon surface. To produce these ordered structures, it is necessary to anneal the surface to 450°C. As the coverage is increased above 0.05 ML, the rows grow in length and number until the surface forms a periodic array of such structures at 0.25 ML. A statistical analysis of the rows reveals a linear increase in median row length as a function of coverage. With regard to their electronic behavior, STS measurements show a significantly narrower band gap along the Ag rows than is found on the underlying silicon structures. Therefore, the deposited Ag atoms do retain some metallic behavior.  相似文献   

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Redox enzymes, which catalyze electron transfer reactions in living organisms, can be used as selective and sensitive bioreceptors in biosensors, or as efficient catalysts in biofuel cells. In these bioelectrochemical devices, the enzymes are immobilized at a conductive surface, the electrode, with which they must be able to exchange electrons. Different physicochemical methods have been coupled to electrochemistry to characterize the enzyme-modified electrochemical interface. In this Review, we summarize most efforts performed to investigate the enzymatic electrodes at the micro- and even nanoscale, thanks to microscopy techniques. Contrary to electrochemistry, which gives only a global information about all processes occurring at the electrode surface, microscopy offers a spatial resolution. Several techniques have been implemented; mostly scanning probe microscopies like atomic force microscopy, scanning tunneling microscopy, and scanning electrochemical microscopy, but also scanning electron microscopy and fluorescence microscopy. These studies demonstrate that various information can be obtained thanks to microscopy at different scales. Electrode imaging has been performed to confirm the presence of enzymes, to quantify and localize the biomolecules, but also to evaluate the morphology of immobilized enzymes, their possible conformation changes upon turnover, and their orientation at the electrode surface. Local redox activity has also been imaged and kinetics has been resolved.  相似文献   

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Tuning the electron transport at the molecular scale is a key step in realizing functional electronic components for molecular electronics, and ongoing interest aims at achieving a higher modulation ratio for single-molecular transistors. Here, a feasible strategy that connects the redox-active moieties with conjugated chains is proposed to improve the electrochemical gating efficiency of molecular junctions in ionic liquid. Benefiting from the low energy barrier height between the Fermi level of the electrode and the frontier molecular orbitals, the conductance of C=C−Fc−Py is about one order of magnitude larger and the conductance on/off ratio shows 160 % improvement compared to that of C−C−Fc−Py at the equilibrium potential of Fc+/Fc. This work provides a new way to design high-performance molecular devices.  相似文献   

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《化学:亚洲杂志》2017,12(21):2772-2779
Single‐molecule magnets (SMMs) exhibiting slow relaxation of magnetization of purely molecular origin are highly attractive owing to their potential applications in spintronic devices, high‐density information storage, and quantum computing. In particular, lanthanide SMMs have been playing a major role in the advancement of this field because of the large intrinsic magnetic anisotropy of lanthanide metal ions. Herein, some recent breakthroughs that are changing the perspective of the field are highlighted, with special emphasis on synthetic strategies towards the design of high‐performance SMMs.  相似文献   

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Nucleation and growth of two‐dimensional Ge nanoclusters on the Si(111)‐(7 × 7) surface at elevated substrate temperatures have been studied using scanning tunneling microscopy. The uniformity of the Ge nanoclusters is improved with the increase of substrate temperature, and ordered Ge nanoclusters are formed on the faulted and unfaulted halves of (7 × 7) unit cell at substrate temperature of 200 °C. It is proposed that the Ge nanoclusters consist of six Ge atoms with three on top of the center adatoms and others on the rest atoms within one half of a unit cell. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

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1 INTRODUCTION Metalloporphyrins are intensively studied for many reasons. They have been comprehensively used in biochemistry, analytical chemistry and so on. They play an important role in biological processes such as oxygen transport photosynthesis and enzyme catalysis. They can act as catalysts[1], and can undergo reversible redox reactions in which the site of electron transfer may be localized on the por- phyrin ring or on the central metal ion. Both reaction types are important in…  相似文献   

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The use of scanning tunneling microscopy (STM) for atomic scale characterization of clean and adsorbate covered (single-crystalline) metal surfaces is discussed. Topographic images reveal details on their periodic structure and on the atomic arrangement in the surface layer, and in particular on surface defects. The observation and characterization of individual adsorbate species gives access to the local electronic structure of the adsorption complex and to details of the chemical bond between substrate and adsorbate. Atomic resolution imaging opens new perspectives for the investigation of various surface processes such as surface diffusion, thin film growth or surface reactions.  相似文献   

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