Self-assembled monolayers (SAMs) represent an important tool in context of nanofabrication and molecular engineering of surfaces and interfaces. The properties of functional SAMs depend not only on the character of the tail groups at the SAM-ambient interface, but are also largely defined by their structure. In its turn, the latter parameter results from a complex interplay of the structural forces and a variety of other factors, including so called odd-even effects, viz. dependence of the SAM structure and properties on the parity of the number (odd or even) of individual building blocks in the backbone of the SAM constituents. The most impressive manifestation of the odd-even effects is the structure of aryl-substituted alkanethiolate SAMs on Au(111) and Ag(111), in which, in spite of the fact that the intermolecular interaction is mostly determined by the aryl part of the monolayers, one observes a pronounced dependence of molecular inclination and, consequently, the packing density of the SAM-forming molecules on the parity of number of methylene units in the alkyl linker. Here we review the properties of the above systems as well as address fundamental reasons behind the odd-even effects, including the existence of a so-called bending potential, which is frequently disregarded in analysis of the structure-building forces. The generality of the odd-even effects in SAMs is additionally supported by the recent data for SAMs on GaAs, scanning tunneling microscopy data for SAMs on Ag(111), and the data for the monolayers with selenolate and carboxyl anchoring groups on Au(111) and Ag(111). The implications of these effects in terms of the control over the packing density and orientation of the tail groups at the SAM-ambient interface, structural perfection, polymorphism, temperature-driven phase transitions, and SAM stability toward such factors as ionizing radiation, exchange reaction, and electrochemical desorption are discussed. These implications place the odd-even effects as an important tool for the design of functional SAMs in context of specific applications.

All-cis-hexafluoro- and all-cis-pentafluoro-cyclohexane (PFCH) derivatives are new kinds of materials, the structures and properties of which are dominated by the highly dipolar Janus-face motif. Here, we report on the effects of integrating the PFCH groups into self-assembled monolayers (SAMs) of alkanethiolates on Au(111). Monolayers with an odd (eleven) and even (twelve) number of methylene groups were characterized in detail by several complementary experimental tools, supported by theoretical calculations. Surprisingly, all the data show a high similarity of both kinds of monolayers, nearly lacking the typically observed odd-even effects. These new monolayers have a packing density about 1/3 lower than that of non-substituted alkanethiolate monolayers, caused by the bulkiness of the PFCH moieties. The orientations of the PFCH groups and the alkyl chains could be determined independently, suggesting a conformation similar to the one found in the solid state structure of an analogous compound. Although in the SAMs the PFCH groups are slightly tilted away from the surface normal with the axial fluorine atoms pointing downwards, most of the dipole moments of the group remain oriented parallel to the surface, which is a unique feature for a SAM system. The consequences are much lower water contact angles compared to other partly fluorinated SAMs as well as rather moderate work function values. The interaction between the terminal PFCH moieties results in an enhanced stability of the PFCH-decorated SAMs toward exchange reaction with potential molecular substituents in spite of the lower packing density of these films.

A series of molecules with oligophenylene backbone, thiolate anchoring group, and pentafluoro-λ⁶-sulfanyl (−SF₅) tail group was synthesized and used as precursors to form self-assembled monolayers (SAMs) on Au(111) substrates. The resulting SAMs feature dense molecular packing, upright molecular orientation, and chemically homogeneous SAM-ambient interface, comprised entirely of the −SF₅ moieties. These SAMs exhibit exceptional wetting and electrostatic properties, showing advancing water contact angles up to 103° and work function values up to 5.96 eV—probably the highest values reported for any aromatic monolayers on gold. They also feature a comparably low value of the tunnelling decay coefficient (0.38 ± 0.07 Å⁻¹), typical of oligophenylene backbone, which is not affected by the introduction of the −SF₅ group. The latter also hardly affects the current densities at a specific bias compared to analogous monolayers with other electronegative tail groups. The superior electrostatic and good charge transport properties of the designed, SF₅-terminated SAMs make them potentially useful for interface engineering in organic electronics and photovoltaics.