Linker dependent bond rupture force measurements in single-molecule junctions

We use a modified conducting atomic force microscope to simultaneously probe the conductance of a single-molecule junction and the force required to rupture the junction formed by alkanes terminated with four different chemical link groups which vary in binding strength and mechanism to the gold electrodes. Molecular junctions with amine, methylsulfide, and diphenylphosphine terminated molecules show clear conductance signatures and rupture at a force that is significantly smaller than the measured 1.4 nN force required to rupture the single-atomic gold contact. In contrast, measurements with a thiol terminated alkane which can bind covalently to the gold electrode show conductance and force features unlike those of the other molecules studied. Specifically, the strong Au-S bond can cause structural rearrangements in the electrodes, which are accompanied by substantial conductance changes. Despite the strong Au-S bond and the evidence for disruption of the Au structure, the experiments show that on average these junctions also rupture at a smaller force than that measured for pristine single-atom gold contacts.     

Effect of anchoring groups on single-molecule conductance: comparative study of thiol-, amine-, and carboxylic-acid-terminated molecules

We studied the effect of anchoring groups on the conductance of single molecules using alkanes terminated with dithiol, diamine, and dicarboxylic-acid groups as a model system. We created a large number of molecular junctions mechanically and analyzed the statistical distributions of the conductance values of the molecular junctions. Multiple sets of conductance values were found in each case. The I-V characteristics, temperature independence, and exponential decay of the conductance with the molecular length all indicate tunneling as the conduction mechanism for these molecules. The prefactor of the exponential decay function, which reflects the contact resistance, is highly sensitive to the anchoring group, and the decay constant is weakly dependent on the anchoring group. These observations are attributed to different electronic couplings between the molecules and the electrodes and alignments of the molecular energy levels relative to the Fermi energy level of the electrodes introduced by different anchoring groups. For diamine and dicarboxylic-acid groups, the conductance values are sensitive to pH due to protonation and deprotonation of the anchoring groups. Further insight into the binding strengths of these anchoring groups to gold electrodes is obtained by statistically analyzing the stretching length of molecular junctions.     

Destructive quantum interference in heterocyclic alkanes: the search for ultra-short molecular insulators

Designing highly insulating sub-nanometer molecules is difficult because tunneling conductance increases exponentially with decreasing molecular length. This challenge is further enhanced by the fact that most molecules cannot achieve full conductance suppression with destructive quantum interference. Here, we present results for a series of small saturated heterocyclic alkanes where we show that conductance is suppressed due to destructive interference. Using the STM-BJ technique and density functional theory calculations, we confirm that their single-molecule junction conductance is lower than analogous alkanes of similar length. We rationalize the suppression of conductance in the junctions through analysis of the computed ballistic current density. We find there are highly symmetric ring currents, which reverse direction at the antiresonance in the Landauer transmission near the Fermi energy. This pattern has not been seen in earlier studies of larger bicyclic systems exhibiting interference effects and constitutes clear-cut evidence of destructive σ-interference. The finding of heterocyclic alkanes with destructive quantum interference charts a pathway for chemical design of short molecular insulators using organic molecules.

We present a combined experimental and theoretical study of small saturated heterocyclic alkanes and show that they perform well as insulators with an electronic transmission that is suppressed due to destructive interference.     

Silver Makes Better Electrical Contacts to Thiol‐Terminated Silanes than Gold

We report that the single‐molecule junction conductance of thiol‐terminated silanes with Ag electrodes are higher than the conductance of those formed with Au electrodes. These results are in contrast to the trends in the metal work function Φ(Ag)<Φ(Au). As such, a better alignment of the Au Fermi level to the molecular orbital of silane that mediates charge transport would be expected. This conductance trend is reversed when we replace the thiols with amines, highlighting the impact of metal–S covalent and metal–NH₂ dative bonds in controlling the molecular conductance. Density functional theory calculations elucidate the crucial role of the chemical linkers in determining the level alignment when molecules are attached to different metal contacts. We also demonstrate that conductance of thiol‐terminated silanes with Pt electrodes is lower than the ones formed with Au and Ag electrodes, again in contrast to the trends in the metal work‐functions.     

Highly conducting π-conjugated molecular junctions covalently bonded to gold electrodes

We measure electronic conductance through single conjugated molecules bonded to Au metal electrodes with direct Au-C covalent bonds using the scanning tunneling microscope based break-junction technique. We start with molecules terminated with trimethyltin end groups that cleave off in situ, resulting in formation of a direct covalent σ bond between the carbon backbone and the gold metal electrodes. The molecular carbon backbone used in this study consist of a conjugated π system that has one terminal methylene group on each end, which bonds to the electrodes, achieving large electronic coupling of the electrodes to the π system. The junctions formed with the prototypical example of 1,4-dimethylenebenzene show a conductance approaching one conductance quantum (G(0) = 2e(2)/h). Junctions formed with methylene-terminated oligophenyls with two to four phenyl units show a 100-fold increase in conductance compared with junctions formed with amine-linked oligophenyls. The conduction mechanism for these longer oligophenyls is tunneling, as they exhibit an exponential dependence of conductance on oligomer length. In addition, density functional theory based calculations for the Au-xylylene-Au junction show near-resonant transmission, with a crossover to tunneling for the longer oligomers.     

Thermodynamics of Mixtures Containing Organic Carbonates. Part XV. Application of the Kirkwood-Buff Theory to the Study of Interactions in Liquid Mixtures Containing Dialkyl Carbonates and Alkanes,Benzene, CCl4 or 1-Alkanols

Binary liquid mixtures containing a dialkyl carbonate (dimethyl or diethyl carbonate) and organic solvents such as alkanes, benzene, CCl₄, or 1-alkanols were studied within the framework of the Kirkwood-Buff formalism. The Kirkwood-Buff integrals, linear coefficients of preferential solvation and local mole fractions were calculated. Results were interpreted assuming that the mixtures with alkanes or 1-alkanols are not random mixtures, which can be ascribed to the existence of strong dipolar interactions between like molecules. Systems containing benzene or CCl₄ are both random and more ordered because of the charge transfer or dipole/induced dipole interactions between the polar group of the solute (O–CO–O) and the polarizable solvent molecules. The effect of increasing temperature was also examined.     

Conductive molecular silicon

Bulk silicon, the bedrock of information technology, consists of the deceptively simple electronic structure of just Si-Si σ bonds. Diamond has the same lattice structure as silicon, yet the two materials have dramatically different electronic properties. Here we report the specific synthesis and electrical characterization of a class of molecules, oligosilanes, that contain strongly interacting Si-Si σ bonds, the essential components of the bulk semiconductor. We used the scanning tunneling microscope-based break-junction technique to compare the single-molecule conductance of these oligosilanes to those of alkanes. We found that the molecular conductance decreases exponentially with increasing chain length with a decay constant β = 0.27 ± 0.01 ?(-1), comparable to that of a conjugated chain of C═C π bonds. This result demonstrates the profound implications of σ conjugation for the conductivity of silicon.     

First-principles electronic transport calculations in finite elongated systems: a divide and conquer approach

We present a first-principles method for the evaluation of the transmittance probability and the coherent conductance through elongated systems composed of a repeating molecular unit and terminated at both ends. Our method is based on a divide and conquer approach in which the Hamiltonian of the elongated system can be represented by a block tridiagonal matrix, and therefore can be readily inverted. This allows us to evaluate the transmittance and the conductance using first-principles electronic structure methods without explicitly performing calculations involving the entire system. A proof of concept model based on a trans-polyacetylene chain bridging two aluminum leads indicates that our divide and conquer approach is able to capture all the features appearing in the transmittance probability curves obtained by a full scale calculation.     

Physicochemistry of Mixed Systems of Water/AOT (Surfactant)/Alkanol (Cosurfactant)/Cycloalkanone (Oil): A Detailed Study of Phase Behavior,Salt Effect,and Conductance Properties

Water in oil microemulsion (μE) systems comprising water/AOT ± alkanol (n-butanol to n-dodecanol)/cycloalkanone (cyclopentanone to cycloheptanone, CA5, CA6, and CA7) were physicochemically studied with respect to phase and conductance behaviors. In absence of alkanols, AOT produced large clear zone with the cycloalkanones, compared to linear alkanes. Clear zone was comprised of gel, viscous, and clear fluid. Alkanols increased the fluidity of μE while its clarity was reduced. A maximum two-phase region was observed for n-heptanol (also for formulations with n-octanol). Salts, which reduced the clarity of the μE, followed the order of effectivity: Na⁺ < Mg²⁺ < Al³⁺. A correlation between clarity and turbidity was found irrespective of molecular size of oil, cosurfactant and salt. The influence of water and temperature on the conductance behavior of W/O formulations was studied. The studied systems were found to be less conducting than those with linear alkanes. Energetics and other structural parameters of the studied systems were evaluated from conductance behavior and the use of scaling equations.     

Activation of dimethyl ether with transition metal atoms

The cocondensation of iron or manganese atoms with dimethyl ether at ?196°C leads to organometallic products which upon hydrolysis at 25°C yield a mixture of mainly alkenes and alkanes.     

A Novel Route to α,ω‐Bis(acrylamidopeptide)‐Terminated Oligo(ethylene oxide) and Hydrogels

A new family of α,ω‐bis(acrylamidopeptide)‐terminated macromonomers were prepared via the ring‐opening addition of 4,4‐dimethyl‐2‐vinyl‐ and 2‐isopropenyl‐4,4‐dimethyl‐oxazol‐5‐on to α,ω‐diamine‐terminated poly(ethylene oxide). These macromonomers were used to produce hydrogels by means of thermally induced free‐radical polymerization. Swelling behavior and mechanical properties of the resulting hydrogels were influenced by the macromonomer type and the crosslinking density, as reflected by the equilibrium water uptake.     

Solvent‐Free Photooxidation of Alkanes by Dioxygen with 2,3‐Dichloro‐5,6‐dicyano‐p‐benzoquinone via Photoinduced Electron Transfer

Photooxidation of alkanes by dioxygen occurred under visible light irradiation of 2,3‐dichloro‐5,6‐dicyano‐p‐benzoquinone (DDQ) which acts as a super photooxidant. Solvent‐free hydroxylation of cyclohexane and alkanes is initiated by electron transfer from alkanes to the singlet and triplet excited states of DDQ to afford the corresponding radical cations and DDQ^??, as revealed by femtosecond laser‐induced transient absorption measurements. Alkane radical cations readily deprotonate to produce alkyl radicals, which react with dioxygen to afford alkylperoxyl radicals. Alkylperoxyl radicals abstract hydrogen atoms from alkanes to yield alkyl hydroperoxides, accompanied by regeneration of alkyl radicals to constitute the radical chain reactions, so called autoxidation. The radical chain is terminated in the bimolecular reactions of alkylperoxyl radicals to yield the corresponding alcohols and ketones. DDQ^??, produced by the photoinduced electron transfer from alkanes to the excited state of DDQ, disproportionates with protons to yield DDQH₂.     

Activation of dimethyl ether with barium and strontium atoms

Organometallic compounds are produced when barium and strontium atoms are cocondensed with dimethyl ether at ?196°C; hydrolysis of the cocondensation products from both reactions yields mainly C₁—C₈ alkanes, alkenes, and alkynes.     

多嵌段共聚物磺酸盐离子导体的合成、结构及导电特性

合成了系列环氧乙烷-(对苯二甲酸乙二酯-CO-间苯二甲酸乙二酯磺酸钠)多嵌段共聚物(EOTM-SO₃Na),用NMR、WAXD和DSC等方法进行了结构表征。EOTM-SO₃Na是一种新型的单阳离子导体,室温电导率可达2.3×10^-6S·cm^-1。     

Hemilabile Ligands as Mechanosensitive Electrode Contacts for Molecular Electronics

Single‐molecule junctions that are sensitive to compression or elongation are an emerging class of nanoelectromechanical systems (NEMS). Although the molecule–electrode interface can be engineered to impart such functionality, most studies to date rely on poorly defined interactions. We focused on this issue by synthesizing molecular wires designed to have chemically defined hemilabile contacts based on (methylthio)thiophene moieties. We measured their conductance as a function of junction size and observed conductance changes of up to two orders of magnitude as junctions were compressed and stretched. Localised interactions between weakly coordinating thienyl sulfurs and the electrodes are responsible for the observed effect and allow reversible monodentate?bidentate contact transitions as the junction is modulated in size. We observed an up to ≈100‐fold sensitivity boost of the (methylthio)thiophene‐terminated molecular wire compared with its non‐hemilabile (methylthio)benzene counterpart and demonstrate a previously unexplored application of hemilabile ligands to molecular electronics.     

Synthesis of ω‐phosphonated poly(ethylene oxide)s through the combination of kabachnik–fields reaction and “click” chemistry

The synthesis of new ω‐phosphonic acid‐terminated poly(ethylene oxide) (PEOs) monomethyl ethers was investigated by the combination of Atherton–Todd or Kabachnik–Fields reactions and the “click” copper‐catalyzed 1,3‐dipolar cycloaddition of azides and terminal alkynes. The Atherton–Todd route fails to give the corresponding phosphonic acid‐terminated PEOs due to competitive cleavage of the P? N bond during the dealkylation step. In contrast, the Kabachnik–Fields route leads with very good yields to ω‐phosphonic acid‐PEO through “click” reaction of azido‐PEO onto dimethyl aminopropargyl phosphonate prepared by Kabachnik–Fields reaction between propargylbenzylimine and dimethyl phosphonate, followed by acidic hydrolysis. The reported methodology, precluding the use of anionic polymerization of ethylene oxide, leads to novel well‐defined phosphonic acid‐terminated PEOs from commercially available products in good yields. Moreover, such a strategy can be adapted to anchor phosphonic acid functionality onto a wide range of polymers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

First-principles calculation on the conductance of a single 1,4-diisocyanatobenzene molecule with single-walled carbon nanotubes as the electrodes

The conductance of a single 1,4-diisocyanatobenzene molecule sandwiched between two single-walled carbon nanotube (SWCNT) electrodes are studied using a fully self-consistent ab initio approach which combines nonequilibrium Green's function formalism with density functional theory calculations. Several metallic zigzag and armchair SWCNTs with different diameters are used as electrodes; dangling bonds at their open ends are terminated with hydrogen atoms. Within the energy range of a few eV of the Fermi energy, all the SWCNT electrodes couple strongly only with the frontier molecular orbitals that are related to nonlocal pi bonds. Although the chirality of SWCNT electrodes has significant influences on this coupling and thus the molecular conductance, the diameter of electrodes, the distance, and the torsion angle between electrodes have only minor influences on the conductance, showing the advantage of using SWCNTs as the electrodes for molecular electronic devices.     

Self-inhibition or the lack of it in the pyrolyses of neopentane and n-hexane

Published data show that in its early stages (up to 3% decomposition), the pyrolysis of n-hexane in the ranges 723–823 K and 10–100 Torr is not inhibited by the olefin products, in contrast with neopentane pyrolysis which is very strongly inhibited in similar conditions. Detailed consideration of the chain mechanisms for the two pyrolyses shows that the reactivity of the chain terminating radical towards hydrogen abstraction from an allylic C? H bond in product olefin is the factor which determines whether or not observable self-inhibition occurs. Thus, n-hexane pyrolysis, whose chain decomposition is terminated by recombination and disproportionation of ethyl, is not significantly self-inhibited, whereas that of neopentane which is terminated by recombination of methyl is very strongly inhibited because methyl is 14× more reactive than ethyl. The implications for other alkanes are briefly discussed.     

Dynamics of the interaction of vapor-deposited copper with alkanethiolate monolayers: bond insertion, complexation, and penetration pathways

We have investigated the interaction of vapor-deposited copper with -CH3, -OH, -OCH3, -COOH, and -CO2CH3 terminated alkanethiolate self-assembled monolayers (SAMs) adsorbed on polycrystalline Au using time-of-flight secondary ion mass spectrometry and density functional theory calculations. For -OH, -COOH, and -CO2CH3 terminated SAMs measurements indicate that for all copper coverages there is a competition between Cu atom bond insertion into C-O bonds, stabilization at the SAM/vacuum interface, and penetration to the Au/S interface. In contrast, on a -OCH3 terminated SAM Cu only weakly interacts with the methoxy group and penetrates to the Au substrate, while for a -CH3 terminated SAM deposited copper only penetrates to the Au/S interface. The insertion of copper into C-O terminal group bonds is an activated process. We estimate that the barriers for Cu insertion are 55 +/- 5 kJ mol(-1) for the ester, 50 +/- 5 kJ mol(-1) for the acid, and 55 +/- 5 kJ mol(-1) for the hydroxyl terminated SAMs. The activation barrier for the copper insertion is much higher for the -OCH3 SAM. Copper atoms with energies lower than the activation barrier partition between complexation (weak interaction) with the terminal groups and penetration through the monolayer to the Au/S interface. Weakly stabilized copper atoms at the SAM/vacuum interface slowly penetrate through the monolayer. In contrast to the case of Al deposition, C-O bond insertion is favored over C=O, C-H, and C-C bond insertion.     

Selective Oxidative Dehydrogenation of Ethane and Propane over Copper-Containing Mordenite: Insights into Reaction Mechanism and Product Protection

Copper(II)-containing mordenite (CuMOR) is capable of activation of C−H bonds in C₁-C₃ alkanes, albeit there are remarkable differences between the functionalization of ethane and propane compared to methane. The reaction of ethane and propane with CuMOR results in the formation of ethylene and propylene, while the reaction of methane predominantly yields methanol and dimethyl ether. By combining in situ FTIR and MAS NMR spectroscopies as well as time-resolved Cu K-edge X-ray absorption spectroscopy, the reaction mechanism was derived, which differs significantly for each alkane. The formation of ethylene and propylene proceeds via oxidative dehydrogenation of the corresponding alkanes with selectivity above 95 % for ethane and above 85 % for propane. The formation of stable π-complexes of olefins with Cu^I sites, formed upon reduction of Cu^II-oxo species, protects olefins from further oxidation and/or oligomerization. This is different from methane, the activation of which proceeds via oxidative hydroxylation leading to the formation of surface methoxy species bonded to the zeolite framework. Our findings constitute one of the major steps in the direct conversion of alkanes to important commodities and open a novel research direction aiming at the selective synthesis of olefins.