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Single-molecule electrical junctions possess a molecular core connected to source and drain electrodes via anchor groups, which feed and extract electricity from specific atoms within the core. As the distance between electrodes increases, the electrical conductance typically decreases, which is a feature shared by classical Ohmic conductors. Here we analyze the electrical conductance of cycloparaphenylene (CPP) macrocycles and demonstrate that they can exhibit a highly nonclassical increase in their electrical conductance as the distance between electrodes increases. We demonstrate that this is due to the topological nature of the de Broglie wave created by electrons injected into the macrocycle from the source. Although such topological states do not exist in isolated macrocycles, they are created when the molecule is in contact with the source. They are predicted to be a generic feature of conjugated macrocycles and open a new avenue to implementing highly nonclassical transport behavior in molecular junctions.
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ConspectusDuring the past decade or so, research groups around the globe have sought to answer the question: "How does electricity flow through single molecules?" In seeking the answer to this question, a series of joint theory and experimental studies have demonstrated that electrons passing through single-molecule junctions exhibit exquisite quantum interference (QI) effects, which have no classical analogues in conventional circuits. These signatures of QI appear even at room temperature and can be described by simple quantum circuit rules and a rather intuitive magic ratio theory. The latter describes the effect of varying the connectivity of electrodes to a molecular core and how electrical conductance can be controlled by the addition of heteroatoms to molecular cores. The former describes how individual moieties contribute to the overall conductance of a molecule and how the overall conductance can change when the connectivities between different moieties are varied. Related circuit rules have been derived and demonstrated, which describe the effects of connectivity on Seebeck coefficients of organic molecules. This simplicity arises because when a molecule is placed between two electrodes, charge transfer between the molecule and electrodes causes the molecular energy levels to adjust, such that the Fermi energy (EF) of the electrodes lies within the energy gap between the highest occupied molecular orbital and lowest unoccupied molecular orbital. Consequently, when electrons of energy EF pass through a molecule, their phase is protected and transport takes place via phase-coherent tunneling. Remarkably, these effects have been scaled up to self-assembled monolayers of molecules, thereby creating two-dimensional materials, whose room temperature transport properties are controlled by QI. This leads to new molecular design strategies for increasing the on/off conductance ratio of molecular switches and to improving the performance of organic thermoelectric materials. In particular, destructive quantum interference has been shown to improve the Seebeck coefficient of organic molecules and increase their on/off ratio under the influence of electrochemical gating. The aim of this Account is to introduce the novice reader to these signatures of QI in molecules, many of which have been identified in joint studies involving our theory group in Lancaster University and experimental group in Bern University.
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In Fig. 1 of this Letter, there should have been two nitrogen (N) atoms at the 1,3-positions of all the blue chemical structures (next to the oxygen atoms), rather than one at the 2-position. The figure has been corrected online, and the original incorrect figure is shown as Supplementary Information to the accompanying Amendment.
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Graphene, a single-layer network of carbon atoms, has outstanding electrical and mechanical properties 1 . Graphene ribbons with nanometre-scale widths2,3 (nanoribbons) should exhibit half-metallicity 4 and quantum confinement. Magnetic edges in graphene nanoribbons5,6 have been studied extensively from a theoretical standpoint because their coherent manipulation would be a milestone for spintronic 7 and quantum computing devices 8 . However, experimental investigations have been hampered because nanoribbon edges cannot be produced with atomic precision and the graphene terminations that have been proposed are chemically unstable 9 . Here we address both of these problems, by using molecular graphene nanoribbons functionalized with stable spin-bearing radical groups. We observe the predicted delocalized magnetic edge states and test theoretical models of the spin dynamics and spin-environment interactions. Comparison with a non-graphitized reference material enables us to clearly identify the characteristic behaviour of the radical-functionalized graphene nanoribbons. We quantify the parameters of spin-orbit coupling, define the interaction patterns and determine the spin decoherence channels. Even without any optimization, the spin coherence time is in the range of microseconds at room temperature, and we perform quantum inversion operations between edge and radical spins. Our approach provides a way of testing the theory of magnetism in graphene nanoribbons experimentally. The coherence times that we observe open up encouraging prospects for the use of magnetic nanoribbons in quantum spintronic devices.
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Electrodes play an essential role in controlling electrode-molecule coupling. However, conventional metal electrodes require linkers to anchor the molecule. Van der Waals interaction offers a versatile strategy to connect the electrode and molecule without anchor groups. Except for graphene, the potential of other materials as electrodes to fabricate van der Waals molecular junctions remains unexplored. Herein, we utilize semimetallic transition metal dichalcogenides (TMDCs) 1T'-WTe2 as electrodes to fabricate WTe2/metalated tetraphenylporphyrin (M-TPP)/WTe2 junctions via van der Waals interaction. Compared with chemically bonded Au/M-TPP/Au junctions, the conductance of these M-TPP van der Waals molecular junctions is enhanced by â¼736%. More importantly, WTe2/M-TPP/WTe2 junctions exhibit the tunable conductance from 10-3.29 to 10-4.44 G0 (1.15 orders of magnitude) via single-atom control, recording the widest tunable range of conductance for M-TPP molecular junctions. Our work demonstrates the potential of two-dimensional TMDCs for constructing highly tunable and conductive molecular devices.
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The thermoelectric properties of molecular junctions consisting of a metal Pt electrode contacting [60]fullerene derivatives covalently bound to a graphene electrode have been studied by using a conducting-probe atomic force microscope (c-AFM). The [60]fullerene derivatives are covalently linked to the graphene via two meta-connected phenyl rings, two para-connected phenyl rings, or a single phenyl ring. We find that the magnitude of the Seebeck coefficient is up to nine times larger than that of Au-C60-Pt molecular junctions. Moreover, the sign of the thermopower can be either positive or negative depending on the details of the binding geometry and on the local value of the Fermi energy. Our results demonstrate the potential of using graphene electrodes for controlling and enhancing the thermoelectric properties of molecular junctions and confirm the outstanding performance of [60]fullerene derivatives.
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There are several binding groups used within molecular electronics for anchoring molecules to metal electrodes (e.g., R-SMe, R-NH2, R-CS2 -, R-S-). However, some anchoring groups that bind strongly to electrodes have poor/unknown stability, some have weak electrode coupling, while for some their binding motifs are not well defined. Further binding groups are required to aid molecular design and to achieve a suitable balance in performance across a range of properties. We present an in-depth investigation into the use of carbodithioate esters as contact groups for single-molecule conductance measurements, using scanning tunnelling microscopy break junction measurements (STM-BJ) and detailed surface spectroscopic analysis. We demonstrate that the methyl carbodithioate ester acts as an effective contact for gold electrodes in STM-BJ measurements. Surface enhanced Raman measurements demonstrate that the C=S functionality remains intact when adsorbed on to gold nanoparticles. A gold(I) complex was also synthesised showing a stable C=SâAuI interaction from the ester. Comparison with a benzyl thiomethyl ether demonstrates that the C=S moiety significantly contributes to charge transport in single-molecule junctions. The overall performance of the CS2Me group demonstrates it should be used more extensively and has strong potential for the fabrication of larger area devices with long-term stability.
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Dipoles are widely involved in π-π interactions and are central to many chemical and biological functions, but their influence on the strength of π-π interactions remains unclear. Here, we report a study of π-π interaction between azulene-based, polar single molecules and between naphthalene-based, nonpolar single molecules. By performing scanning tunneling microscopy break junction measurements of single-molecule conductance, we show that the π-stacked dimers formed by the azulene-based, polar aromatic structures feature higher electrical conductivity and mechanical stability than those formed by the naphthalene-based, nonpolar molecules. Mechanical control of π-π interactions in both rotational and translational motion reveals a sensitive dependence of the stacking strength on relative alignment between the dipoles. The antiparallel alignment of the dipoles was found to be the optimal stacking configuration that underpins the observed enhancement of π-π stacking between azulene-based single molecules. Density functional theory calculations further explained the observed enhancement of stacking strength and the corresponding charge transport efficiency. Our experimental and theoretical results show that the antiparallel alignment of the dipole moments significantly enhances the electronic coupling and mechanical stability of π-π stacking. In addition, in the formation of single-molecule junctions, the azulene group was experimentally and theoretically proved to form a Au-π contact with electrodes with high charge transport efficiency. This paper provides evidence and interpretation of the role of dipoles in π-π interactions at the single-molecule level and offers new insights into potential applications in supramolecular devices.
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Since the early days of quantum mechanics, it has been known that electrons behave simultaneously as particles and waves, and now quantum electronic devices can harness this duality. When devices are shrunk to the molecular scale, it is unclear under what conditions does electron transmission remain phase-coherent, as molecules are usually treated as either scattering or redox centers, without considering the wave-particle duality of the charge carrier. Here, we demonstrate that electron transmission remains phase-coherent in molecular porphyrin nanoribbons connected to graphene electrodes. The devices act as graphene Fabry-Pérot interferometers and allow for direct probing of the transport mechanisms throughout several regimes. Through electrostatic gating, we observe electronic interference fringes in transmission that are strongly correlated to molecular conductance across multiple oxidation states. These results demonstrate a platform for the use of interferometric effects in single-molecule junctions, opening up new avenues for studying quantum coherence in molecular electronic and spintronic devices.
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In-memory computing provides an opportunity to meet the growing demands of large data-driven applications such as machine learning, by colocating logic operations and data storage. Despite being regarded as the ultimate solution for high-density integration and low-power manipulation, the use of spin or electric dipole at the single-molecule level to realize in-memory logic functions has yet to be realized at room temperature, due to their random orientation. Here, we demonstrate logic-in-memory operations, based on single electric dipole flipping in a two-terminal single-metallofullerene (Sc2C2@Cs(hept)-C88) device at room temperature. By applying a low voltage of ±0.8 V to the single-metallofullerene junction, we found that the digital information recorded among the different dipole states could be reversibly encoded in situ and stored. As a consequence, 14 types of Boolean logic operation were shown from a single-metallofullerene device. Density functional theory calculations reveal that the non-volatile memory behaviour comes from dipole reorientation of the [Sc2C2] group in the fullerene cage. This proof-of-concept represents a major step towards room-temperature electrically manipulated, low-power, two-terminal in-memory logic devices and a direction for in-memory computing using nanoelectronic devices.
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Molecular thin films, such as self-assembled monolayers (SAMs), offer the possibility of translating the optimised thermophysical and electrical properties of high-Seebeck-coefficient single molecules to scalable device architectures. However, for many scanning probe-based approaches attempting to characterise such SAMs, there remains a significant challenge in recovering single-molecule equivalent values from large-area films due to the intrinsic uncertainty of the probe-sample contact area coupled with film damage caused by contact forces. Here we report a new reproducible non-destructive method for probing the electrical and thermoelectric (TE) properties of small assemblies (10-103) of thiol-terminated molecules arranged within a SAM on a gold surface, and demonstrate the successful and reproducible measurements of the equivalent single-molecule electrical conductivity and Seebeck values. We have used a modified thermal-electric force microscopy approach, which integrates the conductive-probe atomic force microscope, a sample positioned on a temperature-controlled heater, and a probe-sample peak-force feedback that interactively limits the normal force across the molecular junctions. The experimental results are interpreted by density functional theory calculations allowing quantification the electrical quantum transport properties of both single molecules and small clusters of molecules. Significantly, this approach effectively eliminates lateral forces between probe and sample, minimising disruption to the SAM while enabling simultaneous mapping of the SAMs nanomechanical properties, as well as electrical and/or TE response, thereby allowing correlation of the film properties.
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Ouro , Nanotecnologia , Propriedades de Superfície , Microscopia de Força Atômica/métodos , Condutividade ElétricaRESUMO
Organic thermoelectric materials have potential for wearable heating, cooling, and energy generation devices at room temperature. For this to be technologically viable, high-conductance (G) and high-Seebeck-coefficient (S) materials are needed. For most semiconductors, the increase in S is accompanied by a decrease in G. Here, using a combined experimental and theoretical investigation, we demonstrate that a simultaneous enhancement of S and G can be achieved in single organic radical molecules, thanks to their intrinsic spin state. A counterintuitive quantum interference (QI) effect is also observed in stable Blatter radical molecules, where constructive QI occurs for a meta-connected radical, leading to further enhancement of thermoelectric properties. Compared to an analogous closed-shell molecule, the power factor is enhanced by more than 1 order of magnitude in radicals. These results open a new avenue for the development of organic thermoelectric materials operating at room temperature.
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Quantum-tunneling-based nanoelectronics has the potential for the miniaturization of electronics toward the sub-5 nm scale. However, the nature of phase-coherent quantum tunneling leads to the rapid decays of the electrical conductance with tunneling transport distance, especially in organic molecule-based nanodevices. In this work, we investigated the conductance of the single-cluster junctions of a series of atomically well-defined silver nanoclusters, with varying sizes from 0.9 to 3.0 nm, using the mechanically controllable break junction (MCBJ) technique combined with quantum transport theory. Our charge transport investigations of these single-cluster junctions revealed that the conductance grows with increasing cluster size. The conductance decay constant was determined to be â¼-0.4 nm-1, which is of opposite sign to that of organic molecules. Comparison between experiment and theory reveals that although charge transport through the silver single-cluster junctions occurs via phase-coherent tunneling, this is compensated by a rapid decrease in the energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital (HOMO-LUMO gap) with size and the increase in the electrode-cluster coupling, which results in their conductance increase up to lengths of â¼3.0 nm. These results demonstrate that such families of nanoclusters provide unique bottom-up building blocks for the fabrication of nanodevices in the sub-5 nm size range.
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Stacking interactions are of significant importance in the fields of chemistry, biology, and material optoelectronics because they determine the efficiency of charge transfer between molecules and their quantum states. Previous studies have proven that when two monomers are π-stacked in series to form a dimer, the electrical conductance of the dimer is significantly lower than that of the monomer. Here, we present a strong opposite case that when two anthanthrene monomers are π-stacked to form a dimer in a scanning tunneling microscopic break junction, the conductance increases by as much as 25 in comparison with a monomer, which originates from a room-temperature quantum interference. Remarkably, both theory and experiment consistently reveal that this effect can be reversed by changing the connectivity of external electrodes to the monomer core. These results demonstrate that synthetic control of connectivity to molecular cores can be combined with stacking interactions between their π systems to modify and optimize charge transfer between molecules, opening up a wide variety of potential applications ranging from organic optoelectronics and photovoltaics to nanoelectronics and single-molecule electronics.
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Grafite , Condutividade Elétrica , Eletrodos , Eletrônica , Microscopia de Tunelamento , PolímerosRESUMO
This paper describes the syntheses of several functionalized dihydropyrene (DHP) molecular switches with different substitution patterns. Regioselective nucleophilic alkylation of a 5-substituted dimethyl isophthalate allowed the development of a workable synthetic protocol for the preparation of 2,7-alkyne-functionalized DHPs. Synthesis of DHPs with surface-anchoring groups in the 2,7- and 4,9-positions is described. The molecular structures of several intermediates and DHPs were elucidated by X-ray single-crystal diffraction. Molecular properties and switching capabilities of both types of DHPs were assessed by light irradiation experiments, spectroelectrochemistry, and cyclic voltammetry. Spectroelectrochemistry, in combination with density functional theory (DFT) calculations, shows reversible electrochemical switching from the DHP forms to the cyclophanediene (CPD) forms. Charge-transport behavior was assessed in single-molecule scanning tunneling microscope (STM) break junctions, combined with density functional theory-based quantum transport calculations. All DHPs with surface-contacting groups form stable molecular junctions. Experiments show that the molecular conductance depends on the substitution pattern of the DHP motif. The conductance was found to decrease with increasing applied bias.
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Molecules capable of mediating charge transport over several nanometers with minimal decay in conductance have fundamental and technological implications. Polymethine cyanine dyes are fascinating molecular wires because up to a critical length, they have no bond-length alternation (BLA) and their electronic structure resembles a one-dimensional free-electron gas. Beyond this threshold, they undergo a symmetry-breaking Peierls transition, which increases the HOMO-LUMO gap. We have investigated cationic cyanines with central polymethine chains of 5-13 carbon atoms (Cy3+-Cy11+). The absorption spectra and crystal structures show that symmetry breaking is sensitive to the polarity of the medium and the size of the counterion. X-ray crystallography reveals that Cy9·PF6 and Cy11·B(C6F5)4 are Peierls distorted, with high BLA at one end of the π-system, away from the partially delocalized positive charge. This pattern of BLA distribution resembles that of solitons in polyacetylene. The single-molecule conductance is essentially independent of molecular length for the polymethine salts of Cy3+-Cy11+ with the large B(C6F5)4- counterion, but with the PF6- counterion, the conductance decreases for the longer molecules, Cy7+-Cy11+, because this smaller anion polarizes the π-system, inducing a symmetry-breaking transition. At higher bias (0.9 V), the conductance of the shorter chains, Cy3+-Cy7+, increases with length (negative attenuation factor, ß = -1.6 nm-1), but the conductance still drops in Cy9+ and Cy11+ with the small polarizing PF6- counteranion.
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The most probable single-molecule conductance of each member of a series of 12 conjugated molecular wires, 6 of which contain either a ruthenium or platinum center centrally placed within the backbone, has been determined. The measurement of a small, positive Seebeck coefficient has established that transmission through these molecules takes place by tunneling through the tail of the HOMO resonance near the middle of the HOMO-LUMO gap in each case. Despite the general similarities in the molecular lengths and frontier-orbital compositions, experimental and computationally determined trends in molecular conductance values across this series cannot be satisfactorily explained in terms of commonly discussed "single-parameter" models of junction conductance. Rather, the trends in molecular conductance are better rationalized from consideration of the complete molecular junction, with conductance values well described by transport calculations carried out at the DFT level of theory, on the basis of the Landauer-Büttiker model.
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The experimental investigation of side-chain effects on intramolecular charge transport in π-conjugated molecules is essential but remains challenging. Herein, the dependence of intra-molecular conductance on the nature of branching alkyl chains is investigated through a combination of the scanning tunneling microscope break junction (STM-BJ) technique and density functional theory. Three thiophene-flanked diketopyrrolopyrrole (DPP) derivatives with different branching alkyl chains (isopentane, 3-methylheptane, and 9-methylnonadecane) are used with phenylthiomethyl groups as the anchoring groups. The results of single-molecule conductance measurements show that as the alkyl chain becomes longer, the torsional angles between the aromatic rings increase due to steric crowding, and therefore, the molecular conductance of DPP decreases due to reduction in conjugation. Both theoretical simulations and 1 H NMR spectra demonstrate that the planarity of the DPPs is directly reduced after introducing longer branching alkyl chains, which leads to a reduced conductance. This work indicates that the effect of the insulating side chain on the single-molecule conductance cannot be neglected, which should be considered for the design of future organic semiconducting materials.
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Although methods for a periodic perforation and heteroatom doping of graphene sheets have been developed, patterning closely spaced holes on the nanoscale in graphene nanoribbons is still a challenging task. In this work, nitrogen-doped porous graphene nanoribbons (N-GNRs) were synthesized on Ag(111) using a silver-assisted Ullmann polymerization of brominated tetrabenzophenazine. Insights into the hierarchical reaction pathways from single molecules toward the formation of one-dimensional organometallic complexes and N-GNRs are gained by a combination of scanning tunneling microscopy (STM), atomic force microscopy (AFM) with CO-tip, scanning tunneling spectroscopy (STS), and density functional theory (DFT).
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The realization of self-assembled molecular-electronic films, whose room-temperature transport properties are controlled by quantum interference (QI), is an essential step in the scale-up of QI effects from single molecules to parallel arrays of molecules. Recently, the effect of destructive QI (DQI) on the electrical conductance of self-assembled monolayers (SAMs) has been investigated. Here, through a combined experimental and theoretical investigation, we demonstrate chemical control of different forms of constructive QI (CQI) in cross-plane transport through SAMs and assess its influence on cross-plane thermoelectricity in SAMs. It is known that the electrical conductance of single molecules can be controlled in a deterministic manner, by chemically varying their connectivity to external electrodes. Here, by employing synthetic methodologies to vary the connectivity of terminal anchor groups around aromatic anthracene cores, and by forming SAMs of the resulting molecules, we clearly demonstrate that this signature of CQI can be translated into SAM-on-gold molecular films. We show that the conductance of vertical molecular junctions formed from anthracene-based molecules with two different connectivities differ by a factor of approximately 16, in agreement with theoretical predictions for their conductance ratio based on CQI effects within the core. We also demonstrate that for molecules with thioether anchor groups, the Seebeck coefficient of such films is connectivity dependent and with an appropriate choice of connectivity can be boosted by â¼50%. This demonstration of QI and its influence on thermoelectricity in SAMs represents a critical step toward functional ultra-thin-film devices for future thermoelectric and molecular-scale electronics applications.