Probing Charge Transport of Ruthenium-Complex-Based Molecular Wires at the Single-Molecule Level

A ruthenium(II) bis(sigma-arylacetylide)-complex-based molecular wire functionalized with thiolacetyl alligator clips at both ends (OPERu) was used to fabricate gold substrate-molecular wire-conductive tip junctions. To elucidate the ruthenium-complex-enhanced charge transport, we conducted a single-molecule level investigation using the technique-combination method, where electronic delay constant, single-molecular conductance, and barrier height were obtained by scanning tunneling microscopy (STM) apparent height measurements, STM break junction measurements, and conductive probe-atomic force microscopy (CP-AFM) measurements, respectively.

A novel nanometer-scale "gold electrode-molecular wires-silver" junction: An efficient test bed for electrochemical investigation of electron transportation through molecular wires in self-assembled monolayers

A novel "gold electrode-molecular wires-silver" junction was facilely fabricated for electrochemical study on the electron transportation through molecular wires. Rapid electron transportation through this sandwich-like structure was indeed observed by cyclic voltammograms and ac impedance measurements. Since rather reproducible and reliable results are easily available by electrochemical techniques, it would be an efficient and reliable test bed for electrochemical investigation of charge transportation through molecular wires in self-assembled monolayers on electrodes.

Column chromatographic purification free synthesis of long-chain monodisperse oligo(1,4-phenyleneethynylene)s: towards large-scale automatic synthesis of molecular wires

A facile, mild and rapid solid phase synthetic route free of column chromatographic purification to the synthesis of soluble monodisperse long-chain oligo(1,4-phenyleneethynylene)s is presented.

A rapid solid-phase synthesis to soluble oligothiophene molecular wires

A novel method for the preparation of oligothiophene molecular wires is described via a bi-directional solid-phase synthesis. Using an alternating sequence of bromination and Stille coupling reactions, oligomers were obtained up to the heptamer in excellent yield and purity.

Metal-containing molecular wires and their electron transportation properties

Metal-containing conjugated bisthioester 1 was synthesized. It was fabricated into "gold electrode - molecular wires monolayers - gold nanoparticles" junction using self-assembly and nanoparticles deposition techniques. The junction is suitable for investigating the electron transportation property of molecular wires.

From Tunneling to Hopping: A Comprehensive Investigation of Charge Transport Mechanism in Molecular Junctions Based on Oligo(p-phenylene ethynylene)s

The charge transport mechanism of oligo(p-phenylene ethynylene)s with lengths ranging from 0.98 to 5.11 nm was investigated using modified scanning tunneling microscopy break junction and conducting probe atomic force microscopy methods. The methods were based on observing the length dependence of molecular resistance at single molecule level and the current-voltage characteristics in a wide length distribution. An intrinsic transition from tunneling to hopping charge transport mechanism was observed near 2.75 nm. A new transitional zone was observed in the long length molecular wires compared to short ones. This was not a simple transition between direct tunneling and field emission, which may provide new insights into transport mechanism investigations. Theoretical calculations provided an essential explanation for these phenomena in terms of molecular electronic structures.

Dynamics of quantum dissipation systems interacting with fermion and boson grand canonical bath ensembles: Hierarchical equations of motion approach

A hierarchical equations of motion formalism for a quantum dissipation system in a grand canonical bath ensemble surrounding is constructed on the basis of the calculus-on-path-integral algorithm, together with the parametrization of arbitrary non-Markovian bath that satisfies fluctuation-dissipation theorem. The influence functionals for both the fermion or boson bath interaction are found to be of the same path integral expression as the canonical bath, assuming they all satisfy the Gaussian statistics. However, the equation of motion formalism is different due to the fluctuation-dissipation theories that are distinct and used explicitly. The implications of the present work to quantum transport through molecular wires and electron transfer in complex molecular systems are discussed. (c) 2007 American Institute of Physics.

A partially incoherent rate theory of long-range charge transfer in deoxyribose nucleic acid

A quantum chemistry based Green's function formulation of long-range charge transfer in deoxyribose nucleic acid (DNA) double helix is proposed. The theory takes into account the effects of DNA's electronic structure and its incoherent interaction with aqueous surroundings. In the implementation, the electronic tight-binding parameters for unsolvated DNA molecules are determined at the HF/6-31G* level, while those for individual nucleobase-water couplings are at a semiempirical level by fitting with experimental redox potentials. Numerical results include that: (i) the oxidative charge initially at the donor guanine site does hop sequentially over all guanine sites; however, the revealed rates can be of a much weaker distance dependence than that described by the ordinary Ohm's law; (ii) the aqueous surroundings-induced partial incoherences in thymine/adenine bridge bases lead them to deviate substantially from the superexchange regime; (iii) the time scale of the partially incoherent hole transport through the thymine/adenine pi stack in DNA is about 5 ps. (C) 2002 American Institute of Physics.

苯乙炔类分子导线的合成、组装及电子传输性能

分子导线作为未来分子电子器件的重要组成部分，其合成，组装及电子传输性能研究是当今化学、物理、生物和微电子工程等领域里一个非常热门的研究课题。本论文在齐聚苯乙炔及齐聚苯乙炔一唾吩乙炔分子导线的合成、组装及电子传输性能研究方面进行了一些工作，主要成果有以下几个方面：一、官能化短链分子导线的合成与表征比较系统地合成不同端基，不同分子长度和不同主链结构的乙酞琉基官能化的齐聚苯乙炔类分子导线，以便比较系统地研究各种因素对这类分子导线的自组装及电子传输性能的影响。对所有合成的官能化分子导线进行了红外光谱、核磁共振氢谱和质谱表征以确定其结构。二、长链分子导线的合成与表征用溶液和固定相快速合成方法合成了一系列苯乙炔齐聚物及苯乙炔一（蜜份乙炔交替共聚齐聚物：1）采用简便的路线，用溶液和固定相方法快速合成出十二烷氧基取代的苯乙炔齐聚物，最一长达到了八聚体。（2）采用一条最简便的路线，用固定相方法快速合成了异丙基取代的苯乙炔齐聚物，最长达到了八聚体。（3）用溶液和固定相方法首次合成了苯乙炔一唾吩乙炔交替共聚齐聚物。（4）用一种新颖的“现场去保护／偶联”二倍速方案快速合成出十二烷氧基取代的苯乙炔齐聚物，最长达到了八聚体。该方案最大的优点在于无需分离出对空气敏感的芳香端炔化合物，从而简化了实验操作以及提高了产物的纯度。对所有合成的齐聚物进行了红外光谱、核磁共振氢谱、核磁共振碳谱和激光质谱表征以确定其结构。三、官能化分子导线的组装及电子传输性能研究（l）用STM和CP-AFM研究了合成的官能化分子导线在金基底的自组装行为，发现形成的自组装单层缺陷很少，而且自组装单层非常均一。（2）用电化学和导电原子力显微镜技术研究了上述官能化齐聚苯乙炔分子导线的电子传输性能，发现界面接触和分子长度对分子导线的电子传导能力有很大的影响，而链结构的影响则相对要小些。此外，我们还发现齐聚苯乙炔体系的电子传输衰减系数β值仅为0.19A-1，说明它是一类性能优异的分子导线侯选物。（3）通过量子化学计算，我们对实验结果进行了初步解释。

Rapid solution and solid phase synthesis of monodisperse oligo[(1,4-phenyleneethynylene)-alt-(2,5-thiopheneethynylene)]s

Monodisperse oligo[(1,4-phenyleneethynylene)-alt-(2,5-thiopheneethynylene)]s, new candidates for molecular wires, were rapidly synthesized via an iterative divergent/convergent doubling strategy in solution as well as on Merrifield's resin.

Synthesis and characterization of ferrocene-terminated ruthenium phenylacetylide complexes with alligator clips

Ferrocene-terminated trans/Ru(dppm)(2) (dppm=Ph2PCH2PPh2)-contained molecular wires with alligator clips were prepared. They are suitable for self-assembly on gold electrode to investigate the influence of metal incorporation on the electron transportation property of the molecular wires.

A one-pot procedure to prepare S-protected 4-iodothiophenols

By means of non-aqueous reduction of pipsyl chloride followed by treatment with K2CO3 and then reacting with acetyl chloride or benzyl chloride, S-acetyl/benzyl -4-iodothiophenols were obtained in a one-pot procedure with yield as high as 90%. These S-protected arenethiols are very important intermediates to synthesize self-assembled molecular wires.

Size effects on the melting of nickel nanowires: a molecular dynamics study

The melting process of nickel nanowires are simulated by using molecular dynamics with the quantum Sutten-Chen many-body force field. The wires studied were approximately cylindrical in cross-section and periodic boundary conditions were applied along their length; the atoms were arranged initially in a face-centred cubic structure with the [0 0 1] direction parallel to the long axis of the wire. The size effects of the nanowires on the melting temperatures are investigated. We find that for the nanoscale regime, the melting temperatures of Ni nanowires are much lower than that of the bulk and are linear with the reciprocal of the diameter of the nanowire. When a nanowire is heated up above the melting temperature, the neck of the nanowire begins to arise and the diameter of neck decreases rapidly with the equilibrated running time. Finally, the breaking of nanowire arises, which leads to the formation of the spherical clusters. (C) 2004 Elsevier B.V. All rights reserved.

Quantum Confinement Effects and Electronic Properties of SnO2 Quantum Wires and Dots

On the basis of the density functional theory (DFT) within local density approximations (LDA) approach, we calculate the band gaps for different size SnO2 quantum wire (QWs) and quantum dots (QDs). A model is proposed to passivate the surface atoms of SnO2 QWs and QDs. We find that the band gap increases between QWs and bulk evolve as Delta E-g(wire) = 1.74/d(1.20) as the effective diameter d decreases, while being Delta E-g(dot) = 2.84/d(1.26) for the QDs. Though the similar to d(1.2) scale is significantly different from similar to d(2) of the effective mass result, the ratio of band gap increases between SnO2 QWs and QDs is 0.609, very close to the effective mass prediction. We also confirm, although the LDS calculations underestimate the band gap, that they give the trend of band gap shift as much as that obtained by the hybrid functional (PBE0) with a rational mixing of 25% Fock exchange and 75% of the conventional Perdew-Burke-Ernzerhof (PBE) exchange functional for the SnO2 QWs and QDs. The relative deviation of the LDA calculated band gap difference Lambda E-g compared with the corresponding PBE0 results is only within 5%. Additionally, it is found the states of valence band maximum (VBM) and conduction band minimum (CBM) of SnO2 QWs or QDs have a mostly p- and s-like envelope function symmetry, respectively, from both LDA and PBE0 calculations.

Structural and optical properties of InAs/In0.52Al0.48As self-assembled quantum wires on InP(001)

Six-stacked InAs/In0.52Al0.48As self-assembled quantum wires (QWRs) on InP(001) by molecular-beam epitaxy (MBE) have been studied by high-resolution transmission electron microscopy (HRTEM) and polarized PL measurements. We obtained the chemical lattice fringe (CLF) image of InAs self-assembled QWRs embedded in the In0.52Al0.48As matrix by the interference between the (002)-diffracted beam and the transmitted beam in the image plane of the objective lens. The results show that the InAs QWRs were bounded by (113), (001) and (114) facets. Both the size and strain distribution in QWRs were determined. It was found that with the growth of successive periods, the height and height fluctuation of InAs QWRs decreased from the bottom period to the upper one. Some suggestions are put forward for further improving the uniformity of the stacked InAs QWRs. (c) 2005 Elsevier B.V. All rights reserved.