Self-Assembled Monolayers Derived from Bidentate Organosulfur Adsorbates

The adsorption of a series of 1,2-bis(mercaptomethyl)-4,5-dialkylbenzenes ( 1 ), spiroalkanedithiols ( 2 ), and aliphatic dithiocarboxylic acids (3) on gold yielded new types of self-assembled monolayers (SAMs). The new SAMs were characterized by optical ellipsometry, contact angle goniometry, and polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS). These results were compared to those obtained from SAMs derived from normal alkanethiols ( 4 ) of analogous chain length. Comparisons of ellipsometric thickness and contact angle wettability showed that the new SAMs were well packed and highly oriented. Comparisons of the PM-IRRAS data showed that the SAMs generated from 1 and 2 exhibited slightly less crystallinity than their alkanethiolate-based analogs, while the SAMs generated from 3 exhibited comparable crystallinity to their alkanethiolate-based analogs. Moreover, the SAMs derived from 1 and 2 showed no “odd-even” wettability or PM-IRRAS effects, while those derived from 3 showed remarkably large “odd-even” effects compared to those derived from normal alkanethiols.