Polymeric Self-Assembled Monolayers. 4. Chemical, Electrochemical, and Thermal Stability of ω-Functionalized, Self-Assembled Diacetylenic and Polydiacetylenic Monolayers

Abstract

Here we contrast the stability of monomeric and photopolymerized self-assembled monolayers (SAMs) containing a diacetylene group (HS(CH 2 ) 10 CtCCtC(CH 2 ) 10 COOH) with SAMs prepared from simple n-alkanethiols. The polymerized SAMs are extremely durable compared to either the n-alkanethiol SAMs or the unpolymerized diacetylenic SAMs. For example, they are stable to repeated electrochemical cycling to extreme potentials, thermal excursions to 200°C, and exposure to hot base (1:1 mixture of ethanol and 1.0 M aqueous KOH at 100°C). All of these conditions completely strip n-alkanethiol SAMs from Au substrates. These high-performance materials are suitable for applications in lubrication, adhesion, corrosion passivation, and chemical sensing.

Surface-Confined Nanoparticles as Substrates for Photopolymerizable Self-Assembled Monolayers

“…Nanoparticle surface-coverage [17] is estimated as~13 % by absorbance measurements, in agreement with coverage determinations for similar systems by transmission electron microscopy (TEM) and atomic force microscopy (AFM). [12] The well-defined order and roughness of the gold nanoparticle monolayers is confirmed by AFM measurements (Fig. 2a).…”

“…[10] PDA SAMs have outstanding stability [12] and, by controlling the molecular architecture of self-assembling molecules, highly conjugated polymers can be obtained. [11] Because the gold substrates for SAMs are most often prepared by evaporation or sputtering, full advantage of the self-assembly technique (i.e., non-restricted geometry) has yet to be exploited.…”

Self‐Assembled Monolayers into the 21st Century: Recent Advances and Applications

“…Therefore we believe the second key trend in research into self-assembled monolayers will be towards the development of more stable self-assembly systems. Certainly some researchers are already directing their attention to the problem of stability through new alkanethiols which increase the forces of attraction between the alkyl chains [48,49,167] or through self-assembly systems which form more robust bonds with the underlying substrate using more attachment points [92,93] or different chemistry [168]. Despite the need for more stable self-assembly systems fortunately many of the concepts developed, and much of the knowledge acquired, using alkanethiol chemistry will be transferable to new selfassembly systems.…”

Bottom-Up Synthesis and Morphological Control of High-Axial-Ratio Nanostructures through Molecular Self-Assembly

“…Only few studies have been reported for the polymerization using monolayer lipid membranes (MLMs) of diacetylene derivatives as a matrix, such as liposomes 88 or multi-layer sheets, 89,90 which highly contrasts to a number of studies on the bilayermembrane (BLM)-templated polymerization. [91][92][93][94][95][96][97] Furthermore, the molecular weights of the polydiacetylne products have been uncertain due to the fairly poor solubility of the polymerized entity. Unidirectional selfassembly along the molecular short axis and subsequent polymerization enabled us to obtain isolated, single poly(diacetylene) chains.…”