Disulfide-Containing Nitrosoarenes: Synthesis and Insights into Their Self-Polymerization on a Gold Surface.

Disulfide-containing nitrosoarenes with [bis(4-nitrosobenzyl) disulfide, ()] or without [4-nitrosophenyl disulfide, (), and 1,2-bis(4'-nitroso-[1,1'-biphenyl]-4-yl)disulfane, ()] an alkyl spacer between the sulfur headgroup and the aromatic moiety (phenyl in () or biphenyl in ()) were synthesized and used as precursors to form azodioxy thiolate films on Au(111) substrates. Due to the incorporated disulfide functionalities, these specifically designed nitrosoarenes are enabled to self-polymerize through azodioxy bonds on a gold surface. Thin films of (), (), and () were prepared at different adsorption times via the solution-phase self-assembly of molecules onto the Au(111) surface and characterized by Raman spectroscopy, ellipsometry, water contact angle measurements, atomic force microscopy (AFM), and scanning tunneling microscopy (STM).