Dependence of an interfacial diels-alder reaction kinetics on the density of the immobilized dienophile: An example of phase-separation

Interfacial reactions kinetics often differ from kinetics of bulk reactions. Here, we describe how the density change of an immobilized reactant influences the kinetics of interfacial reactions. Self-assembled monolayers (SAMs) of alkanethiolates on gold were used as a model interface and the Diels-Alder reaction between immobilized quinones and soluble cyclopentadiene was used as a model reaction. The kinetic behavior was studied using varying concentrations of quinones. An unusual threshold density of quinones (γ_c = 5.2-7.2%), at which the pseudo-first order rate constant started to vary as the reaction progressed, was observed. This unexpected kinetic behavior was attributed to the phase-separation phenomena of multi-component SAMs. Additional experiments using more phase-separated two-component SAMs supported this explanation by revealing a significant decrease in γ_c values. When the background hydroxyl group was replaced with carboxylic or phosphoric acid groups, γ_c was observed at below 1%. Also, more phase-separated thermodynamically controlled SAMs produced a lower critical density (3% < γ_c < 4.9%) than that of the less phaseseparated kinetically controlled SAMs (6.5% < γ_c < 8.9%).