Improving the Binding Characteristics of Tripodal Compounds on Single Layer Graphene

Graphene is an atomically thin, transparent, and conductive electrode material of interest for sensors and energy conversion and storage devices, among others. Fully realizing its potential will require robust and general methods to anchor active functionality onto its pristine basal plane. Such strategies should not utilize covalent bond formation, which disrupts the graphene's π-electron system, from which most of its desirable properties arise. We recently introduced a tripodal binding motif, which forms robust monolayers on graphene capable of immobilizing active proteins and preventing their denaturation. Here we describe structure-property relationships for a series of tripod binding groups with "feet" of different sizes. Each derivative adsorbs strongly (ΔGads ≈ -39 kJ mol(-1)) to graphene's basal plane, yet the resulting monolayers exhibit kinetic stabilities that vary over 2 orders of magnitude and molecular densities that vary by a factor of 2. This study identifies phenanthrene as a superior anchor relative to pyrene on the basis of its increased monolayer density and similar kinetic stability. We also demonstrate that varying the length of the methylene linkers between the feet and tripodal core does not affect binding substantially. These results represent the first demonstration of structure-property relationships in the assembly of molecular adsorbates on graphene and provide a paradigm for designing effective graphene binding motifs.