Para-Fluoro-Thiol Reaction on Anchor Layers Grafted from an Aryldiazonium Salt: A Tool for Surface Functionalization with Thiols

Abstract

A new coupling reaction, the para-fluoro-thiol (PFT) reaction, activated by base at room temperature, is reported for carbon surface functionalization. 4-Nitrothiophenol (4-NTP) and (3-nitrobenzyl)mercaptan (3-NBM) were coupled to penta-fluorophenyl (F-5-Ph) anchor layers grafted from the aryldiazonium ion formed in situ. The relative yields of the PFT reactions, estimated from the electrochemical responses of coupled nitrophenyl (NP) and nitrobenzyl (NB) groups, depended on the nucleophilicity of the thiolate and the strength of the base. The highest surface concentration (4.6 x 10(-10) mol cm(-2)) was obtained using 3-NBM in the presence of [Bu4N]OH; this concentration corresponds to the maximum that is typically achieved for other high-yielding coupling reactions at aryldiazonium ion anchor layers. The PFT reaction is expected to be applicable to the numerous thiol derivatives commonly restricted to self-assembled monolayer (SAM) formation at gold and other noble metals, thereby opening a simple new approach for interface design on carbon substrates. The strategy may also have advantages for modification of gold surfaces: the layer prepared by coupling 3-NBM to F-5-Ph films on gold was found to be more stable to storage under ambient conditions than self-assembled monolayers of 3-NBM.