Phase-dependent premelting of self-assembled phosphonic acid multilayers

Melting and premelting phenomena in self-organized organic systems have been extensively explored in the literature, exploring distinct behaviors of different molecule lengths and morphologies. Nevertheless, the influence of the supramolecular assembly configuration on the occurrence of premelting remains poorly explored. Here we use phosphonic acids as model systems for self-organized molecular assemblies. These molecules exhibit long-range order on different types of substrates. The balance between chain-to-chain and head-to-head interactions leads to distinct types of stackings. Although their structural configurations are well understood, very little is known about their behavior near the melting transition. We show here that premelting occurs in lamellar structures and that its behavior depends directly on the ordered configuration assumed in the studied multilayers. Two molecules with different chain lengths were investigated: octadecyl phosphonic and octyl phosphonic acids. Although almost no dependence on the molecule length was observed, the occurrence of premelting is strongly influenced by their lamellar packing configuration. For tilted packings premelting is unfavored while in straight configurations, where alkyl chain interactions are weakened with respect to head-to-head interactions, strong premelting is observed. We find that the onset of premelting occurs at the domain boundaries with straight lamellar configurations and the domain sizes exhibit power law temperature dependences.