Odd-even effects in aryl-substituted alkanethiolate SAMs: nonsymmetrical attachment of aryl unit and its impact on the SAM structure

Aryl-substituted alkanethiolate (AT) self-assembled monolayers (SAMs) exhibit typically so-called odd-even effects, viz. systematic variations in the film structure, packing density, and molecular inclination depending on the parity of the number of the methylene units in the alkyl linker, n. As an exception to this rule, ATs carrying an anthracen-2-yl group (Ant-n) as tail group were reported to have different behavior due the non-symmetric attachment of the anthracene unit to the AT linker, providing additional degree of freedom for the molecular organization and allowing for partial compensation of the odd-even effects. In this context, the structure of SAMs formed by adsorption of anthracene-substituted ATs (Ant-n; n = 1-6) at room temperature on Au(111) substrate was investigated by high-resolution scanning tunnelling microscopy (STM). Most of these SAMs exhibit a coexistence of two different ordered phases, some of which are common for either n = odd or n = even while other vary over the series, showing a broad variety of different structures. The average packing density of the Ant-n SAMs, derived from the analysis of the STM data, varies by 7.5-10% depending on the parity of n, being, as expected, higher for n = odd. The respective extent of the odd-even effects is noticeably lower than that usually observed for other aryl-substituted monolayers (similar to 25%), which goes in line with the previous findings and emphasizes the impact of the non-symmetric attachment of the aromatic unit. Due to non-symmetric attachment of the anthracene unit to the alkanethiolate linker, the respective monolayers on Au(111) exhibit low extent of the odd-even effects and distinct polymorphism, showing, at the same time, high structural order.