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Quantum interference (QI) plays a crucial role in determining the charge transport in molecular devices. In this work, the efficient modulation of QI in meta‐phenylene ethylene oligomer molecular devices by a double N‐substitution strategy is demonstrated. By altering the positions of two N atoms in the central ring with respect to the connecting sites, the molecular conductance can be tuned by more than one order of magnitude. Theoretical analysis, including magic ratio theory, orbital rule, and transmission simulations, reveals how the two N atoms synergistically modulate the molecule conductance between destructive QI and constructive QI states. Remarkably, addition of a second N atom does not simple reinforce the effect of the first; in contrast, it may completely cancel the effect of the first. Understanding the complex electronic interplay between the two N atoms in double N‐substituted molecules paves a path toward utilization of heterocyclic aromatic hydrocarbons in molecular electronics. [ABSTRACT FROM AUTHOR]

Together with the more intuitive and commonly recognized conductance mechanisms of charge‐hopping and tunneling, quantum‐interference (QI) phenomena have been identified as important factors affecting charge transport through molecules. Consequently, establishing simple and flexible molecular‐design strategies to understand, control, and exploit QI in molecular junctions poses an exciting challenge. Here we demonstrate that destructive quantum interference (DQI) in meta‐substituted phenylene ethylene‐type oligomers (m‐OPE) can be tuned by changing the position and conformation of methoxy (OMe) substituents at the central phenylene ring. These substituents play the role of molecular‐scale taps, which can be switched on or off to control the current flow through a molecule. Our experimental results conclusively verify recently postulated magic‐ratio and orbital‐product rules, and highlight a novel chemical design strategy for tuning and gating DQI features to create single‐molecule devices with desirable electronic functions. [ABSTRACT FROM AUTHOR]

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A key target in molecular electronics has been molecules having switchable electrical properties. Switching between two electrical states has been demonstrated using such stimuli as light, electrochemical voltage, complexation and mechanical modulation. A classic example of the latter is the switching of 4,4′-bipyridine, leading to conductance modulation of around 1 order of magnitude. Here, we describe the use of side-group chemistry to control the properties of a single-molecule electromechanical switch, which can be cycled between two conductance states by repeated compression and elongation. While bulky alkyl substituents inhibit the switching behavior, π-conjugated side-groups reinstate it. DFT calculations show that weak interactions between aryl moieties and the metallic electrodes are responsible for the observed phenomenon. This represents a significant expansion of the single-molecule electronics 'tool-box' for the design of junctions with electromechanical properties. [ABSTRACT FROM AUTHOR]

The compounds and complexes 1,4-C6H4(C≡C- cyclo-3-C4H3S)2 ( 2), trans-[Pt(C≡C- cyclo-3-C4H3S)2(PEt3)2] ( 3), trans-[Ru(C≡C- cyclo-3-C4H3S)2(dppe)2] ( 4; dppe=1,2-bis(diphenylphosphino)ethane) and trans-[Ru(C≡C- cyclo-3-C4H3S)2{P(OEt)3}4] ( 5) featuring the 3-thienyl moiety as a surface contacting group for gold electrodes have been prepared, crystallographically characterised in the case of 3- 5 and studied in metal|molecule|metal junctions by using both scanning tunnelling microscope break-junction (STM-BJ) and STM- I( s) methods (measuring the tunnelling current ( I) as a function of distance ( s)). The compounds exhibit similar conductance profiles, with a low conductance feature being more readily identified by STM- I( s) methods, and a higher feature by the STM-BJ method. The lower conductance feature was further characterised by analysis using an unsupervised, automated multi-parameter vector classification (MPVC) of the conductance traces. The combination of similarly structured HOMOs and non-resonant tunnelling mechanism accounts for the remarkably similar conductance values across the chemically distinct members of the family 2- 5. [ABSTRACT FROM AUTHOR]

To guide the choice of future synthetic targets for single-molecule electronics, qualitative design rules are needed, which describe the effect of modifying chemical structure. Here the effect of heteroatom substitution on destructive quantum interference (QI) in single-molecule junctions is, for the first time experimentally addressed by investigating the conductance change when a 'parent' meta-phenylene ethylene-type oligomer (m-OPE) is modified to yield a 'daughter' by inserting one nitrogen atom into the m-OPE core. We find that if the substituted nitrogen is in a meta position relative to both acetylene linkers, the daughter conductance remains as low as the parent. However, if the substituted nitrogen is in an ortho position relative to one acetylene linker and a para position relative to the other, destructive QI is alleviated and the daughter conductance is high. This behavior contrasts with that of a para-connected parent, whose conductance is unaffected by heteroatom substitution. These experimental findings are rationalized by transport calculations and also agree with recent 'magic ratio rules', which capture the role of connectivity in determining the electrical conductance of such parents and daughters. [ABSTRACT FROM AUTHOR]

We provide a brief overview of recent measurements and predictions of thermoelectric properties of single-molecules and porous nanoribbons and discuss some principles underpinning strategies for enhancing their thermoelectric performance. The latter include (a) taking advantage of steep slopes in the electron transmission coefficient T ( E ) , (b) creating structures with delta-function-like transmission coefficients and (c) utilising step-like features in T ( E ) . To achieve high performance, we suggest that the latter may be the most fruitful, since it is less susceptible to inhomogeneous broadening. For the purpose of extrapolating thermoelectric properties of single or few molecules to monolayer molecular films, we also discuss the relevance of the conductance-weighted average Seebeck coefficient. [ABSTRACT FROM AUTHOR]

Host−guest interactions are of central importance in many biological and chemical processes. However, the investigation of the formation and decomplexation of host−guest systems at the single-molecule level has been a challenging task. Here we show that the single-molecule conductance of organoplatinum(II) metallocycle hosts can be enhanced by an order of magnitude by the incorporation of a C60 guest molecule. Mechanically stretching the metallocycle-C60 junction with a scanning tunneling microscopy break junction technique causes the release of the C60 guest from the metallocycle, and consequently the conductance switches back to the free-host level. Metallocycle hosts with different shapes and cavity sizes show different degrees of flexibility to accommodate the C60 guest in response to mechanical stretching. DFT calculations provide further insights into the electronic structures and charge transport properties of the molecular junctions based on metallocycles and the metallocycle-C60 complexes. Studying the single-molecule behavior of host-guest complexes can provide fundamental insights into their supramolecular interactions. Here, the authors use the scanning tunneling microscopy break junction technique to show that encapsulation of a C60 molecule significantly enhances the conductance of an organoplatinum metallocycle; mechanical stretching of the junction releases the guest, returning the conductance to free-host level. [ABSTRACT FROM AUTHOR]

The effectiveness of five different anchor groups for non‐covalent interfacing to graphene electrodes are compared. A family of six molecules is tested in single‐molecule junctions: five consist of the same porphyrin core with different anchor groups, and the sixth is a reference molecule without anchor groups. The junction formation probability (JFP) has a strong dependence on the anchor group. Larger anchors give higher binding energies to the graphene surface, correlating with higher JFPs. The best anchor groups tested are 1,3,8‐tridodecyloxypyrene and 2,5,8,11,14‐pentadodecylhexa‐peri‐hexabenzocoronene, with JFPs of 36% and 38%, respectively. Many junctions are tested at 77 K for each molecule by measuring source‐drain current as a function of bias and gate voltages. For each compound, there is wide variation in the strength of the electronic coupling to the electrodes and in the location of Coulomb peaks. In most cases, this device‐to‐device variability makes it impossible to observe trends between the anchor and the charge‐transport characteristics. Tetrabenzofluorene anchors, which are not π‐conjugated with the porphyrin, exhibit different charge transport behavior to the other anchors tested, and they show multiple Coulomb peaks with characteristically small molecular electron‐addition energies of 0.3–0.7 eV, whereas the other compounds give single Coulomb peaks. Molecules can be interfaced with graphene electrodes using non‐covalent interactions to generate single‐molecule transistors. A family of π‐stacking anchor groups is synthesized and the yield of transistors depends strongly on the nature of the anchor group. Whilst coupling to electrodes varies between devices, it is possible to identify junctions functionalized with single molecules if they exhibit characteristic addition energies. [ABSTRACT FROM AUTHOR]

The single-molecule conductance of metal complexes of the general forms trans-Ru(CCArCCY)2(dppe)2 and trans-Pt(CCArCCY)2(PPh3)2 (Ar = 1,4-C6H2-2,5-(OC6H13)2; Y = 4-C5H4N, 4-C6H4SMe) have been determined using the STM I(s) technique. The complexes display high conductance (Y = 4-C5H4N, M = Ru (0.4 ± 0.18 nS), Pt (0.8 ± 0.5 nS); Y = 4-C6H5SMe, M = Ru (1.4 ± 0.4 nS), Pt (1.8 ± 0.6 nS)) for molecular structures of ca. 3 nm in length, which has been attributed to transport processes arising from tunneling through the tails of LUMO states. [ABSTRACT FROM AUTHOR]

The single molecule conductances of a series of bis-2,2':6',2"-terpyridine complexes featuring Ru(II), Fe(II), and Co(II) metal ions and trimethylsilylethynyl (Me3SiC=C-) or thiomethyl (MeS-) surface contact groups have been determined. In the absence of electrochemical gating, these complexes behave as tunneling barriers, with conductance properties determined more by the strength of the electrode-molecule contact and the structure of the "linker" than the nature of the metal-ion or redox properties of the complex. [ABSTRACT FROM AUTHOR]

We have investigated a large set of symmetric and asymmetric molecules to demonstrate a general rule for molecular-scale quantum transport, which provides a new route to materials design and discovery. The rule states "the conductance GXBY of an asymmetric molecule is the geometric mean of the conductance of the two symmetric molecules derived from it and the thermopower SXBY of the asymmetric molecule is the algebraic mean of their thermopowers". The studied molecules have a structure X-B-Y, where B is the backbone of the molecule, while X and Y are anchor groups, which bind the molecule to metallic electrodes. When applied to experimentally measured histograms of conductance and thermopower, the rules apply to the statistically most probable values. We investigated molecules with anchors chosen from the following family: cyano, pyridl, dihydrobenzothiol, amine and thiol. For the backbones B, we tested 14 different structures. We found that the formulas (GXBY)2 = GXBX*GYBY and SXBY = (SXBX + SYBY)/2 were satisfied in the large majority of the cases, provided the Fermi energy is located within the HOMO-LUMO gap of the molecules. The circuit rules imply that if measurements are performed on molecules with nA different anchors and nB different backbones, then properties of nA(nA + 1)nB/2 molecules can be predicted. So for example, in the case of 20 backbones and 10 anchors, 30 measurements (or reliable calculations) can provide a near quantitative estimate for 1070 measurements of other molecules, at no extra cost. [ABSTRACT FROM AUTHOR]

We report transport measurements on a graphene-fullerene single-molecule transistor. The device architecture where a functionalized C60 binds to graphene nanoelectrodes results in strong electron-vibron coupling and weak vibron relaxation. Using a combined approach of transport spectroscopy, Raman spectroscopy, and DFT calculations, we demonstrate center-of-mass oscillations, redox-dependent Franck-Condon blockade, and a transport regime characterized by avalanche tunnelling in a single-molecule transistor. [ABSTRACT FROM AUTHOR]

If quantum interference patterns in the hearts of polycyclic aromatic hydrocarbons could be isolated and manipulated, then a significant step toward realizing the potential of single-molecule elec tronics would be achieved. H e re we demonstrate experimentally and theoretically that a simple, parameter-free, analytic theory of interference patterns evaluated at the mid-point of the HOMO--LUMO gap (referred to as Mfunctions) correctly predicts conductance ratios of molecules with pyrene, naphthalene, anthracene, anthanthrene, or azulene hearts. M-functions provide new design strategies for identifying molecules with phase-coherent logic functions and enhancing the sensitivity of molecular-scale interferometers. [ABSTRACT FROM AUTHOR]