Electrochemically Controlled Layer‐by‐Layer Deposition of Metal‐Cluster Molecular Multilayers on Gold

Abstract

The ordered and controlled location of molecular compounds on electrode surfaces is essential for the nanometer-scale design of electrochemical interfaces in view of fundamental electron-transfer studies and several lines of applications, such as molecular electronic devices, optical devices, and sensors.[1] Furthermore, layer-by-layer deposition of molecular units onto preorganized self-assembled monolayers (SAMs) has proven to be useful in preparing layered architectures with enhanced properties.[2] Although a significant progress has been made for atomic-scale depositions (such as underpotential deposition and atomic layer epitaxy) [3] or molecular 2D assembly, [4] an "electrochemicalcontrol strategy" to prepare layer-by-layer 3D structures from molecular building blocks is currently unavailable. Herein we report on the successful construction of layer-by-layer nanostructures on a gold electrode by using a redox-active metalcluster molecule, [5] in which the electrode potential modulation precisely controls the multilayer growth. We show that the series of multilayers display extensive electronic coupling between the linked molecular units, thus allowing facile multielectron transport to occur at interfaces.

Investigation of a novel trinuclear μ-oxo ruthenium complex as a potential nitric oxide releaser for biological purposes

“…In such compounds, the proximity of the ruthenium atoms leads to a strong metal-metal interaction, both magnetic and electronic, enhancing the electron delocalization over the [Ru 3 O] + core, which behaves like a single metal center [24]. Besides the rich redox, electrochromic and catalytic properties, species containing labile and/or bridging ligands can act as building blocks to assemble supramolecular structures [18,19,[24][25][26][27][28]. The [Ru 3 O(CH 3 COO) 6 )] moiety also appears as an appealing unit to react with NO 0 .…”

Photocurrent generation of heterostructured films composed of donor–acceptor and donor–insulator networks on indium-tin-oxide electrodes

“…3,4 Layer-by-layer molecular fabricated films are attractive because all of the films are constructed using chemical bonding. [5][6][7][8][9][10][11][12][13][14] Therefore, we have constructed thin films of transition metal complexes using the layerby-layer fabrication technique. We have previously reported the preparation of single-component ultrathin films of polypyridine ruthenium(II) complexes (RuLn) on glass plates and indium-tin-oxide (ITO) electrodes.…”

Synthesis of an Anthraquinone‐Bridged bis(terpyridine) Ligand and its Use in the Stepwise Fabrication of Complex Oligomer Wires on Gold

“…[1][2][3][4] Selfassembled-monolayers (SAMs) [5][6][7] have been widely used as the modification, and construction of multi-layer structures using reactions on the solid surface have been reported in recent years. [8][9][10][11] Moreover, these layer-by-layer structures are expected to be applied to the construction of nanoscale devices such as dye-sensitized solar cells and organic light-emitting diodes.…”