Electrical molecular switch addressed by chemical stimuli

Audi, Hassib; Viero, Yannick; Alwhaibi, N.; Chen, Z.; Iazykov, Maksym; Heynderickx, A.; Xiao, Fuliang; Guérin, David; Krzeminski, Christophe; Grace, Iain; Lambert, Colin J.; Siri, Olivier; Vuillaume, D.; Lenfant, S.; Klein, Hubert

doi:10.1039/d0nr02461a

Cited by 16 publications

(16 citation statements)

References 74 publications

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“…[ 36 ] for an example of bias‐induced switching in stretched metal nanowires). We do not expect that stimulus to be related to chemical processes, such as protonation; [ 37,38 ] also significant changes in the molecular conformation, like in azobenzene‐based SAMs, [ 39,40 ] are not possible because of the rigid molecular backbones. We can also rule out environmental effects, such as a change in humidity, [ 26 ] since the temperature and humidity did not change noticeably during the experiments.…”

Section: Discussionmentioning

confidence: 99%

Bias‐Triggered Conductivity Switching and High Effective Rectification in Metallocene‐Based Molecular Junctions

Asyuda

Das

Lang

et al. 2022

Adv Elect Materials

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Molecular diodes usually exhibit fixed current values at a specific bias and achieve sizable rectification ratio (RR) at voltages of ≈1.0 V. Here, a series of custom‐designed molecular films of ferrocenyl/ruthenocenyl‐substituted biphenylthiolates and fluorenethiolates on Au (111) is presented, which exhibit a distinctly different behavior. When embedded into two‐terminal junctions, they show two different conduction states, with a high conductivity state at a negative bias and a low conductivity state upon applying a sufficiently high positive bias. Comparing the current values for these two states, an effective RR of more than 1000 is obtained, a value comparable to the best performing molecular diodes but attained already at particularly low voltages. Significantly, the switching between the conduction states is reversible and the initial, high conductivity state can be recovered by the application of a negative bias. The proposed explanation for these observations is the bias‐induced switching of the junction to a metastable state comprising oxidized ferrocenyl/ruthenocenyl entities, which are characterized by less delocalized frontier orbitals and cause the formation of a significant potential barrier within the junction. It is hypothesized that this state can be stabilized by structural changes in the monolayers, affecting also their coupling to the top electrode.

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Section: Discussionmentioning

confidence: 99%

Bias‐Triggered Conductivity Switching and High Effective Rectification in Metallocene‐Based Molecular Junctions

Asyuda

Das

Lang

et al. 2022

Adv Elect Materials

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“…Similarly, other nitrogen heterocyclic molecules, imidazole [ 69 , 70 ] and pyrazole [ 71 , 72 ] have been proven as attractive molecules for forming molecular junctions. They can also provide pH-activated connections between Au electrodes and molecules.…”

Section: Ph Detectionmentioning

confidence: 99%

Recent Advances in Single-Molecule Sensors Based on STM Break Junction Measurements

Zeng

Zhou

et al. 2022

Biosensors

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Single-molecule recognition and detection with the highest resolution measurement has been one of the ultimate goals in science and engineering. Break junction techniques, originally developed to measure single-molecule conductance, recently have also been proven to have the capacity for the label-free exploration of single-molecule physics and chemistry, which paves a new way for single-molecule detection with high temporal resolution. In this review, we outline the primary advances and potential of the STM break junction technique for qualitative identification and quantitative detection at a single-molecule level. The principles of operation of these single-molecule electrical sensing mainly in three regimes, ion, environmental pH and genetic material detection, are summarized. It clearly proves that the single-molecule electrical measurements with break junction techniques show a promising perspective for designing a simple, label-free and nondestructive electrical sensor with ultrahigh sensitivity and excellent selectivity.

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“…Moreover, the significant promise for building logical devices and memories at the molecular level impends to the successful transformation of various conformational or electronic states of photochromic molecules into electrical switching signals. In 2020, Audi et al introduced benzo-bis (imidazole)-based molecular switch addressed by chemical stimuli [22]. By virtue of theoretical calculations which ascribe the various behaviors to the position of the HOMO resonances corresponding to the Fermi energy of the electrodes, a multiscale characterization of the electron transport across the molecular junction upon protonation demonstrated that their conductance switching relies on the lateral functional groups in such molecular switches.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Investigation of Design Methodology, Optimized Molecular Geometries, and Electronic Properties of Benzene-Based Single Molecular Switch with Metal Nanoelectrodes

Tharammal

Kumar²,

Rajak

et al. 2020

Journal of Nanomaterials

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Understanding the electronic properties at the single molecular level is the first step in designing functional electronic devices using individual molecules. This paper proposes a simulation methodology for the design of a single molecular switch. A single molecular switch has two stable states that possess different chemical configurations. The methodology is implemented for 1,4-benzene dithiol (BDT) molecule with gold, silver, platinum, and palladium metal nanoelectrodes. The electronic properties of the designed metal-molecule-metal sandwich structure have been investigated using density functional theory (DFT) and Hartree-Fock (HF) method. It has been perceived that the DFT and HF values are slightly different as HF calculation does not include an electron-electron interaction term. Computation of the switching ratio gives the insight that BDT with gold has a high switching ratio of 0.88 compared with other three metal nanoelectrodes. Further, calculations of quantum chemical descriptors, analysis of the density of states (DOS) spectrum, and frontier molecular orbitals for both the stable states (i.e., ON and OFF state geometries) have been carried out. Exploring the band gap, ionization potential, and potential energy of two stable states reveals that the ON state molecule shows slightly higher conductivity and better stability than the OFF state molecule for every chosen electrode in this work. The proposed methodology for the single molecular switch design suggests an eclectic promise for the application of these new materials in novel single molecular nanodevices.

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Electrical molecular switch addressed by chemical stimuli

Cited by 16 publications

References 74 publications

Bias‐Triggered Conductivity Switching and High Effective Rectification in Metallocene‐Based Molecular Junctions

Bias‐Triggered Conductivity Switching and High Effective Rectification in Metallocene‐Based Molecular Junctions

Recent Advances in Single-Molecule Sensors Based on STM Break Junction Measurements

Theoretical Investigation of Design Methodology, Optimized Molecular Geometries, and Electronic Properties of Benzene-Based Single Molecular Switch with Metal Nanoelectrodes

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