Abstract
Thioester-functionalized, siloxane-anchored, self-assembled monolayers provide a powerful tool for controlling the chemical and physical properties of surfaces. The thioester moiety is relatively stable to long-term storage and its structure can be systematically varied so as to provide a well-defined range of reactivity and wetting properties. The oxidation of thioesters with different-chain-length acyl groups allows for very hydrophobic surfaces to be transformed into very hydrophilic, sulfonic acid-bearing, surfaces. Systematic variation in the length of the polymethylene chain has also allowed us to examine how imbedding reaction sites at various depths in a densely packed monolayer changes their reactivity. π-Systems (benzene and thiophene) conjugated to the thioester carbonyl enable the facile creation of photoreactive surfaces that are able to use light of different wavelengths. These elements of structural diversity combine with the utility of the hydrophilic, strongly negatively charged sulfonate-bearing surface to constitute an important approach to systematic surface modification.
Highlights
Functionalized self-assembled monolayers (SAMs) provide powerful tools for conveniently adjusting the composition and chemistry of solid interfaces
Our laboratory has reported in situ transformations of siloxaneanchored SAMs in which SAM surface functionality was changed from benzene rings to arylsulfonic acids [8,9], from
Trichlorosilane 1a was prepared by a method similar to that reported for its longer chain analogue [15], and compounds 1b–i, 2, 3 and 4 were all produced by hydrosilylation of a terminal olefin that was obtained by acylation of ω-undecenyl thiol, which had been prepared in three steps from commercial ω-undecenol
Summary
Functionalized self-assembled monolayers (SAMs) provide powerful tools for conveniently adjusting the composition and chemistry of solid interfaces. In situ chemical transformations of the SAM surfaces provide an additional dimension to the versatility and utility of the SAMs [4,5,6,7]. Our laboratory has reported in situ transformations of siloxaneanchored SAMs in which SAM surface functionality was changed from benzene rings to arylsulfonic acids [8,9], from. Nitrate esters to hydroxyls [10], and from carboxylate esters to carboxylic acids [11,12]. All three of these functionalized surfaces could not have been deposited directly since the requisite silanes would not have been stable. Layer-by-layer [13] and modular assembly [14] of sulfonic acid surfaces with a lower degree of order and uniformity has been reported
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