Counterion loss from charged surface-bound complexes drives the formation of loosely packed monolayers

The functionality of multicomponent self-assembled monolayers (SAMs) can be severely diminished by the segregation of like components into nanoscale domains, a process that maximizes favorable short-range intermolecular interactions. Here, we explore the use of a modular family of sulfur-functionalized metal bis(terpyridine) complexes ([M(tpy-R)2]2+(PF6–)2) to prepare mixed SAMs, considering that the comparable structure, dimensions, and ionic composition of these species should render them interchangeable within the adsorbed surface layer. While surface voltammetry experiments show these SAMs do exhibit compositions representative of their assembly solutions, they also suggest, in line with previous reports, that adjacent complexes in the monolayer are separated by a gap of ~1 nm. Remarkably, X-ray photoelectron spectroscopy studies reveal no F 1s peak features that would confirm the proliferation of PF6− counterions on the surface. We propose that the loose packed structure of these SAMs results from the loss or exchange of PF6– counterions which introduces significant repulsive Coulomb interactions between the adsorbed 2+ charged complexes. The hypothesis is supported by an electrostatic model which indicates these complexes should form close packed SAMs if mobile counterions are present. First-principles calculations demonstrate that complex-counterion binding interactions are weakened by charge transfer to the gold substrate, suggesting this may play an important role in the formation of such low coverage SAMs. Together, this study raises important questions regarding the assembly, organization, and composition of charged SAMs, and highlights new opportunities in the design of multicomponent monolayer assemblies with free volume, for example, to facilitate surface-based reactions or support molecular switches.