Haixing Li

Stereoelectronic switching in single-molecule junctions

A new intersection between reaction chemistry and electronic circuitry is emerging from the ultraminiaturization of electronic devices. Over decades chemists have developed a nuanced understanding of stereoelectronics to establish how the electronic properties of molecules relate to their conformation; the recent advent of single-molecule break-junction techniques provides the means to alter this conformation with a level of control previously unimagined. Here we unite these ideas by demonstrating the first single-molecule switch that operates through a stereoelectronic effect. We demonstrate this behaviour in permethyloligosilanes with methylthiomethyl electrode linkers. The strong σ conjugation in the oligosilane backbone couples the stereoelectronic properties of the sulfur-methylene σ bonds that terminate the molecule. Theoretical calculations support the existence of three distinct dihedral conformations that differ drastically in their electronic character. We can shift between these three species by simply lengthening or compressing the molecular junction, and, in doing so, we can switch conductance digitally between two states.

Aromaticity decreases single-molecule junction conductance.

We have measured the conductance of single-molecule junctions created with three different molecular wires using the scanning tunneling microscope-based break-junction technique. Each wire contains one of three different cyclic five-membered rings: cyclopentadiene, furan, or thiophene. We find that the single-molecule conductance of these three wires correlates negatively with the resonance energy of the five-membered ring; the nonaromatic cyclopentadiene derivative has the highest conductance, while the most aromatic of this series, thiophene, has the lowest. Furthermore, we show for another wire structure that the conductance of furan-based wires is consistently higher than for analogous thiophene systems, indicating that the negative correlation between conductance and aromaticity is robust. The best conductance would be for a quinoid structure that diminishes aromaticity. The energy penalty for partly adopting the quinoid structure is less with compounds having lower initial aromatic stabilization. An additional effect may reflect the lower HOMOs of aromatic compounds.

Silicon Ring Strain Creates High-Conductance Pathways in Single-Molecule Circuits

Here we demonstrate for the first time that strained silanes couple directly to gold electrodes in break-junction conductance measurements. We find that strained silicon molecular wires terminated by alkyl sulfide aurophiles behave effectively as single-molecule parallel circuits with competing sulfur-to-sulfur (low G) and sulfur-to-silacycle (high G) pathways. We can switch off the high conducting sulfur-to-silacycle pathway by altering the environment of the electrode surface to disable the Au-silacycle coupling. Additionally, we can switch between conductive pathways in a single molecular junction by modulating the tip-substrate electrode distance. This study provides a new molecular design to control electronics in silicon-based single molecule wires.

Electric Field Breakdown in Single Molecule Junctions

Here we study the stability and rupture of molecular junctions under high voltage bias at the single molecule/single bond level using the scanning tunneling microscope-based break-junction technique. We synthesize carbon-, silicon-, and germanium-based molecular wires terminated by aurophilic linker groups and study how the molecular backbone and linker group affect the probability of voltage-induced junction rupture. First, we find that junctions formed with covalent S-Au bonds are robust under high voltage and their rupture does not demonstrate bias dependence within our bias range. In contrast, junctions formed through donor-acceptor bonds rupture more frequently, and their rupture probability demonstrates a strong bias dependence. Moreover, we find that the junction rupture probability increases significantly above ∼1 V in junctions formed from methylthiol-terminated disilanes and digermanes, indicating a voltage-induced rupture of individual Si-Si and Ge-Ge bonds. Finally, we compare the rupture probabilities of the thiol-terminated silane derivatives containing Si-Si, Si-C, and Si-O bonds and find that Si-C backbones have higher probabilities of sustaining the highest voltage. These results establish a new method for studying electric field breakdown phenomena at the single molecule level.

Single-Molecule Conductance in Atomically Precise Germanium Wires

While the electrical conductivity of bulk-scale group 14 materials such as diamond carbon, silicon, and germanium is well understood, there is a gap in knowledge regarding the conductivity of these materials at the nano and molecular scales. Filling this gap is important because integrated circuits have shrunk so far that their active regions, which rely so heavily on silicon and germanium, begin to resemble ornate molecules rather than extended solids. Here we unveil a new approach for synthesizing atomically discrete wires of germanium and present the first conductance measurements of molecular germanium using a scanning tunneling microscope-based break-junction (STM-BJ) technique. Our findings show that germanium and silicon wires are nearly identical in conductivity at the molecular scale, and that both are much more conductive than aliphatic carbon. We demonstrate that the strong donor ability of C-Ge σ-bonds can be used to raise the energy of the anchor lone pair and increase conductance. Furthermore, the oligogermane wires behave as conductance switches that function through stereoelectronic logic. These devices can be trained to operate with a higher switching factor by repeatedly compressing and elongating the molecular junction.

Evaluating atomic components in fluorene wires

Molecular electronics demands complex functional molecules with multiple pathways connecting electrode leads. We report the synthesis and study of a set of molecules based on a fluorene-like design in which atomic connectors are used to introduce two pathways for conductance. This manuscript details the structural demands and underlying rationale for developing high conductance in these complex molecular circuit components.

Silane and Germane Molecular Electronics

This Account provides an overview of our recent efforts to uncover the fundamental charge transport properties of Si-Si and Ge-Ge single bonds and introduce useful functions into group 14 molecular wires. We utilize the tools of chemical synthesis and a scanning tunneling microscopy-based break-junction technique to study the mechanism of charge transport in these molecular systems. We evaluated the fundamental ability of silicon, germanium, and carbon molecular wires to transport charge by comparing conductances within families of well-defined structures, the members of which differ only in the number of Si (or Ge or C) atoms in the wire. For each family, this procedure yielded a length-dependent conductance decay parameter, β. Comparison of the different β values demonstrates that Si-Si and Ge-Ge σ bonds are more conductive than the analogous C-C σ bonds. These molecular trends mirror what is seen in the bulk. The conductance decay of Si and Ge-based wires is similar in magnitude to those from π-based molecular wires such as paraphenylenes However, the chemistry of the linkers that attach the molecular wires to the electrodes has a large influence on the resulting β value. For example, Si- and Ge-based wires of many different lengths connected with a methyl-thiomethyl linker give β values of 0.36-0.39 Å-1, whereas Si- and Ge-based wires connected with aryl-thiomethyl groups give drastically different β values for short and long wires. This observation inspired us to study molecular wires that are composed of both π- and σ-orbitals. The sequence and composition of group 14 atoms in the σ chain modulates the electronic coupling between the π end-groups and dictates the molecular conductance. The conductance behavior originates from the coupling between the subunits, which can be understood by considering periodic trends such as bond length, polarizability, and bond polarity. We found that the same periodic trends determine the electric field-induced breakdown properties of individual Si-Si, Ge-Ge, Si-O, Si-C, and C-C bonds. Building from these studies, we have prepared a system that has two different, alternative conductance pathways. In this wire, we can intentionally break a labile, strained silicon-silicon bond and thereby shunt the current through the secondary conduction pathway. This type of in situ bond-rupture provides a new tool to study single molecule reactions that are induced by electric fields. Moreover, these studies provide guidance for designing dielectric materials as well as molecular devices that require stability under high voltage bias. The fundamental studies on the structure/function relationships of the molecular wires have guided the design of new functional systems based on the Si- and Ge-based wires. For example, we exploited the principle of strain-induced Lewis acidity from reaction chemistry to design a single molecule switch that can be controllably switched between two conductive states by varying the distance between the tip and substrate electrodes. We found that the strain intrinsic to the disilaacenaphthene scaffold also creates two state conductance switching. Finally, we demonstrate the first example of a stereoelectronic conductance switch, and we demonstrate that the switching relies crucially on the electronic delocalization in Si-Si and Ge-Ge wire backbones. These studies illustrate the untapped potential in using Si- and Ge-based wires to design and control charge transport at the nanoscale and to allow quantum mechanics to be used as a tool to design ultraminiaturized switches.

Tuning Conductance in π–σ–π Single-Molecule Wires

While the single-molecule conductance properties of π-conjugated and σ-conjugated systems have been well-studied, little is known regarding the conductance properties of mixed σ-π backbone wires and the factors that control their transport properties. Here we utilize a scanning tunneling microscope-based break-junction technique to study a series of molecular wires with π-σ-π backbone structures, where the π-moiety is an electrode-binding thioanisole ring and the σ-moiety is a triatomic α-β-α chain composed of C, Si, or Ge atoms. We find that the sequence and composition of group 14 atoms in the α-β-α chain dictates whether electronic communication between the aryl rings is enhanced or suppressed. Placing heavy atoms at the α-position decreases conductance, whereas placing them at the β-position increases conductance: for example, the C-Ge-C sequence is over 20 times more conductive than the Ge-C-Ge sequence. Density functional theory calculations reveal that these conductance trends arise from periodic trends (i.e., atomic size, polarizability, and electronegativity) that differ from C to Si to Ge. The periodic trends that control molecular conductance here are the same ones that give rise to the α and β silicon effects from physical organic chemistry. These findings outline a new molecular design concept for tuning conductance in single-molecule electrical devices.

High-Conductance Pathways in Ring-Strained Disilanes by Way of Direct σ-Si–Si to Au Coordination

A highly conducting electronic contact between a strained disilane and Au is demonstrated through scanning tunneling microscope-based single-molecule measurements. Conformationally locked cis diastereomers of bis(sulfide)-anchor-equipped 1,2-disilaacenaphthenes readily form high-conducting junctions in which the two sulfide anchors bind in a bipodal fashion to one gold electrode, providing enough stability for a stable electrical contact between the Si-Si σ bond and the other electrode.

Extreme Conductance Suppression in Molecular Siloxanes

Single-molecule conductance studies have traditionally focused on creating highly conducting molecular wires. However, progress in nanoscale electronics demands insulators just as it needs conductors. Here we describe the single-molecule length-dependent conductance properties of the classic silicon dioxide insulator. We synthesize molecular wires consisting of Si-O repeat units and measure their conductance through the scanning tunneling microscope-based break-junction method. These molecules yield conductance lower than alkanes of the same length and the largest length-dependent conductance decay of any molecular systems measured to date. We calculate single-molecule junction transmission and the complex band structure of the infinite 1D material for siloxane, in comparison with silane and alkane, and show that the large conductance decay is intrinsic to the nature of the Si-O bond. This work highlights the potential for siloxanes to function as molecular insulators in electronics.