Synthesis of N-(n-octyl)-N′-(10-mercaptodecyl)-4,4′-bipyridinium dibromide and electrochemical behaviour of its monolayers on a gold electrode

Yan, Juchao; Li, Jinghong; Chen, Wenqi; Dong, Shaojun

doi:10.1039/ft9969201001

Cited by 16 publications

(7 citation statements)

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“…Thus, the adsorption behavior implied that the Vio molecules organized into a close-packed structure. Indeed, the saturated Γ of the Vio -SAM was estimated to be 4.1 × 10 –10 mol·cm –2 , which agrees with the value reported for the SAMs of n -alkanethiols bearing one viologen unit as the terminal functional group in which the viologen units are perpendicularly oriented to organize close-packed structures. − In contrast, the Γ values of the dendritic molecules ( A1 , A2 , A3 ) saturated within a few minutes, suggesting that the crystallization step based on the van der Waals interaction of the decyl groups did not occur due to the bulky dendritic viologen-arranged terminal group. This adsorption behavior is consistent with the cone array model that expects weak interaction of each decyl unit (Figure a).…”

Section: Resultssupporting

confidence: 83%

Electrostatic Repulsion-Induced Desorption of Dendritic Viologen-Arranged Molecules Anchored on a Gold Surface through a Gold–Thiolate Bond Leading to a Tunable Molecular Template

et al. 2018

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We investigated the adsorption and desorption behavior of self-assembled monolayers (SAMs) on gold derived from dendritic viologen-arranged molecules with an ω-mercaptodecyl group (A n, n (dendritic generation) = 0-3) at the apex of the dendritic structure in polar solvents. The adsorption of the dendritic molecules occurred quickly and saturated within a few minutes in an acetonitrile/ethanol (1/1, v/v) mixture at a concentration of 2 mM. Atomic force microscopy images of the SAMs showed flat surfaces regardless of the dendritic generation because the peripheral viologen units were closely packed at the surface of the molecular layer. Individual A3 molecules immobilized on the substrate were observed by scanning tunneling microscopy measurements of a mixed SAM with decanethiol. The desorption behaviors of dendritic molecules from the A n-SAMs in several solvents such as water were also investigated. The spontaneous desorption of the A n-SAM occurred more rapidly than that of a conventional n-alkanethiol SAM. However, the desorption was inhibited by adding electrolytes such as NaNO due to the shielding effect on the electrostatic repulsion between the dendritic molecules. These results indicate that the surface density of the dendritic molecules can be controlled through the desorption.

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Section: Resultssupporting

confidence: 83%

Electrostatic Repulsion-Induced Desorption of Dendritic Viologen-Arranged Molecules Anchored on a Gold Surface through a Gold–Thiolate Bond Leading to a Tunable Molecular Template

et al. 2018

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“…The surface density of the dendritic molecule ( Γ D ) and the area occupied by one molecule ( S D ) were calculated from Γ V , as summarized in Table 1 . n -Alkanethiols bearing one viologen unit at the head group are known to form well-ordered SAMs on gold substrates, in which the viologen units are perpendicularly oriented to organize close-packed structures and the alkyl chains are loosely packed 12 13 14 15 . The S value of Vio - S AM was estimated to be 40 Å 2 ( Table 1 ), which agrees with the values reported for the aforementioned viologen SAM (38 Å 2 ) 12 13 14 15 and is substantially larger than that of a conventional n -alkanethiol SAM (21.4 Å 2 ) 13 16 .…”

Section: Resultsmentioning

confidence: 99%

Conical Gradient Junctions of Dendritic Viologen Arrays on Electrodes

Kawauchi

Oguchi

Nagai

et al. 2015

Sci Rep

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The three-dimensional construction of arrays of functional molecules on an electrode surface, such as organic semiconductors and redox-active molecules, is a considerable challenge in the fabrication of sophisticated junctions for molecular devices. In particular, well-defined organic layers with precise molecular gradients are anticipated to function as novel metal/organic interfaces with specific electrical properties, such as a space charge layer at the metal/semiconductor interface. Here, we report a strategy for the construction of a three-dimensional molecular array with an electrical connection to a metal electrode by exploiting dendritic molecular architecture. Newly designed dendritic molecules consisting of viologens (1,1′-disubstituted-4,4′-bipyridilium salts) as the framework and mercapto groups as anchor units form unique self-assembled monolayers (SAMs) on a gold surface reflecting the molecular design. The dendritic molecules exhibit a conical shape and closely pack to form cone arrays on the substrate, whereas, in solution, they expand into more flexible conformations. Differences in the introduction position of the anchor units in the dendritic structure result in apical- and basal-type cone arrays in which the spatial concentration of the viologen units can be precisely configured in the cones. The concentration in apical-type SAMs increases away from the substrate, whereas the opposite is true in basal-type SAMs.

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“…Gold–thiolate bonding and multiple van der Waals contacts between the oligomethylene chains are responsible for the formation of a molecular layer on the electrode surface. These fascinating self‐assembly processes have been exploited to prepare electroactive monolayers of bipyridinium compounds on gold 30–35. The building blocks employed for these studies integrate a bipyridinium dication and a thiol group in the same molecular skeleton.…”

Section: Self‐assembling Bipyridinium Monolayersmentioning

confidence: 99%

“…The building blocks employed for these studies integrate a bipyridinium dication and a thiol group in the same molecular skeleton. Compound 12 (Figure 5) is a representative example 32a. It combines the affinity of a terminal thiol group for gold with the electroactive character of the bipyridinium dication and, in fact, self‐assembles on gold electrodes producing electroactive monolayers.…”

Section: Self‐assembling Bipyridinium Monolayersmentioning

confidence: 99%

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Electron transport in bipyridinium films

Raymo

Alvarado

2004

The Chemical Record

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Bipyridinium dications are versatile building blocks for the assembly of functional materials. In particular, their reliable electrochemical response has encouraged the design of electroactive films. Diverse and elegant experimental strategies to coat metallic and semiconducting electrodes with bipyridinium compounds have, in fact, emerged over the past two decades. The resulting interfacial assemblies span from a few nanometers to several micrometers in thickness. They incorporate from a single molecular layer to large collections of entangled polymer chains. They transport electrons efficiently from the electrode surface to the film/solution interface and vice versa. Electron self-exchange between and the physical diffusion of the bipyridinium building blocks conspire in defining the charge transport properties of these fascinating electroactive assemblies. Often, the matrix of electron-deficient bipyridinium dications can be exploited to entrap electron-rich analytes. Electrostatic interactions promote the supramolecular association of the guests with the surface-confined host matrix. Furthermore, chromophoric sites can be coupled to the bipyridinium dications to produce photosensitive arrays capable of harvesting light and generating current. Thus, thorough investigations on the fundamental properties of these functional molecule-based materials can lead to promising applications in electroanalysis and solar energy conversion, while contributing to advances in the basic understanding of electron transport in interfacial assemblies.

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Synthesis of N-(n-octyl)-N′-(10-mercaptodecyl)-4,4′-bipyridinium dibromide and electrochemical behaviour of its monolayers on a gold electrode

Cited by 16 publications

References 31 publications

Electrostatic Repulsion-Induced Desorption of Dendritic Viologen-Arranged Molecules Anchored on a Gold Surface through a Gold–Thiolate Bond Leading to a Tunable Molecular Template

Electrostatic Repulsion-Induced Desorption of Dendritic Viologen-Arranged Molecules Anchored on a Gold Surface through a Gold–Thiolate Bond Leading to a Tunable Molecular Template

Conical Gradient Junctions of Dendritic Viologen Arrays on Electrodes

Electron transport in bipyridinium films

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