A Unified Model: Self-Assembly of Trimesic Acid on Gold

Abstract

Self-assembly of trimesic acid (TMA) displayed remarkable abundance over its full coverage range on gold under ultrahigh vacuum conditions. Experiments showed that previously well-reported “chicken wire” and “flower” structures were actually two special cases within its full coverage. All observed assembling structures formed hexagonal porous networks that could be well-described by a unified model in which the TMA molecules inside the half unit cells (equilateral triangles) were bound via trimeric hydrogen bonds and all half unit cells were connected to each other via dimeric hydrogen bonds. These porous networks possessed pores of 1.1 ± 0.1 nm in diameter, and the interpore distance was tunable from 1.6 nm on at a step size of ∼0.93 nm. Energetics analysis unveiled that the assembling structures less than one molecular layer was optimally driven by maximization of the dimeric hydrogen bonds.