Nanomechanics of Bidentate Thiolate Ligands on Gold Surfaces

Michoff, Martín E. Zoloff; Ribas‐Ariño, Jordi; Marx, Dominik

doi:10.1103/physrevlett.114.075501

Cited by 8 publications

(3 citation statements)

References 64 publications

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“…Moreover, the mechanical stability of catechol–Fe 3+ bonds is also similar to other coordination bonds reported in literature, but are significantly lower than that of covalent bonds. − The mechanical stability of a bond is not just determined by its bond strength. Instead, it is determined by the free energy barrier as well as the position of the transition state.…”

Section: Discussionsupporting

confidence: 78%

Single-Molecule Mechanics of Catechol-Iron Coordination Bonds

Li¹,

Wen²,

Qin³

et al. 2017

ACS Biomater. Sci. Eng.

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Metal coordination bonds are widely found in natural adhesives and load-bearing and protective materials, in which they are thought to be responsible for the high mechanical strength and toughness. However, it remains unknown how metal−ligand complexes could give rise to such superb mechanical properties. Here, we developed a singlechain nanoparticle based force spectroscopy to directly quantify the mechanical properties of individual catechol− Fe 3+ complexes, the key elements accounting for the high toughness and extensibility of byssal threads of marine mussels. We found that catechol−Fe 3+ complexes possess a unique combination of mechanical features, including high mechanical stability, fast reformation kinetics, and stoichiometry-dependent mechanics. Therefore, they can serve as sacrificial bonds to efficiently dissipate energy in the materials, quickly recover the mechanical properties when load is released, and respond to pH and Fe 3+ concentrations. Especially, we revealed that the bis-catechol−Fe 3+ complex is mechanically ∼90% stronger than the tris-catechol−Fe 3+ complex. Quantum calculation study suggested that the distinction between mechanical strength and thermodynamic stability of catechol−Fe 3+ complexes is due to their different mechanical rupture pathways. Our study provides the nanoscale mechanistic understanding of the coordination bond-mediated mechanical properties of biogenetic materials, and could guide future rational design and regulation of the mechanical properties of synthetic materials.

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Section: Discussionsupporting

confidence: 78%

Single-Molecule Mechanics of Catechol-Iron Coordination Bonds

Li¹,

Wen²,

Qin³

et al. 2017

ACS Biomater. Sci. Eng.

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“…In fact, the general physical concepts that describe the way in which an external force accelerates the rate of transition over an energy barrier were first presented at the beginning of the last century by Prandtl and also used by Eyring to model fluid viscosity as well as other mechanically induced processes . They have also been used to describe nanoscale friction measured in the AFM − by the so-called Prandtl-Tomlinson model. , Molecular simulations have been carried out for alkyl thiolate species on coinage metal surfaces ,,− to probe the molecular mechanisms occurring under normal and lateral stresses. Such theoretical studies have suggested that shear of alkyl thiolate-covered silver and gold can occur within the metal substrate and can result in the evolution of metal-containing species, not observed for a pin sliding over copper.…”

Section: Discussionmentioning

confidence: 99%

Modeling Mechanochemical Reaction Mechanisms

Adams

Miller

Furlong

et al. 2017

ACS Appl. Mater. Interfaces

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The mechanochemical reaction between copper and dimethyl disulfide is studied under well-controlled conditions in ultrahigh vacuum (UHV). Reaction is initiated by fast S-S bond scission to form adsorbed methyl thiolate species, and the reaction kinetics are reproduced by two subsequent elementary mechanochemical reaction steps, namely a mechanochemical decomposition of methyl thiolate to deposit sulfur on the surface and evolve small, gas-phase hydrocarbons, and sliding-induced oxidation of the copper by sulfur that regenerates vacant reaction sites. The steady-state reaction kinetics are monitored in situ from the variation in the friction force as the reaction proceeds and modeled using the elementary-step reaction rate constants found for monolayer adsorbates. The analysis yields excellent agreement between the experiment and the kinetic model, as well as correctly predicting the total amount of subsurface sulfur in the film measured using Auger spectroscopy and the sulfur depth distribution measured by angle-resolved X-ray photoelectron spectroscopy.

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“…Integration of bidentate organic linkers can lead to the formation of discrete structures (d = 0) such as molecular complexes or salts. [110][111][112] However, there are very few reports focusing on studies of the electronic properties of these structures. [113] One well-known example is based on the preparation of salts of H 2 AzoBPDC (H 2 AzoBPDC = (E)-4,4′-(diazene-1,2-diyl) dibenzoic acid; c = 2; Figure 14) that were studied for modulating ionic conductivity through azobenzene photoisomerization.…”

Section: Functionalization Of 0d Materials With Photochromic Molecule...mentioning

confidence: 99%

Dynamically Controlled Electronic Behavior of Stimuli‐Responsive Materials: Exploring Dimensionality and Connectivity

Leith

Martin

Mathur

et al. 2021

Advanced Energy Materials

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Materials with dynamically controlled electronic structures (i.e., upon external stimuli) are at the forefront of the renewable energy sector with applications as memory devices, smart supercapacitors, programmable solar cells, and field‐effect transistors. Moreover, their continued development as device components is critical for the field of optoelectronics since their performance is comparable, or could even surpass, the current benchmarks. Adaptive electronic properties are the main focus of this review that discusses recent developments in the modulation of electronic behavior that can be tuned using external stimuli in metal–organic frameworks (MOFs), covalent–organic frameworks (COFs), primarily inorganic hybrids, polymers, and graphitic‐type materials. Triggers to achieve “dynamic” behavior discussed within this manuscript are primarily light‐based switches that include different classes of photochromic molecules such as naphthalene diimide, viologen, diarylethene, azobenzene, and spiropyran. The effect of material dimensionality and photoswitch connectivity achieved through integration of photochromic moieties inside 0D, 1D, 2D, and 3D hybrid matrices is discussed. This review showcases the prospects of advancing the material and energy landscapes through employment of structural motifs with adaptive electronic structures occurring as a function of their dimensionality and connectivity.

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Nanomechanics of Bidentate Thiolate Ligands on Gold Surfaces

Cited by 8 publications

References 64 publications

Single-Molecule Mechanics of Catechol-Iron Coordination Bonds

Single-Molecule Mechanics of Catechol-Iron Coordination Bonds

Modeling Mechanochemical Reaction Mechanisms

Dynamically Controlled Electronic Behavior of Stimuli‐Responsive Materials: Exploring Dimensionality and Connectivity

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