Using trimesic acid (TMA) as a model system by means of scanning tunneling microscope (STM) equipped with a temperature controller, here, we report a temperature-assisted method to cooperatively control electric-field-induced supramolecular phase transitions at the liquid/solid interface. Octanoic acid is used as a solvent due to its good solubility for TMA and its less complicated pattern formed under negative STM bias (e.g., only chicken-wire polymorphs existing). At positive substrate bias, STM revealed that TMA assembly based on temperature modulations underwent phase transitions from a porous (22 °C) to a flower (45 °C) and further to a zigzag (68 °C) structure. The transitions are ascribed to the partial deprotonation of the carboxyl groups of TMA. Both the temperature and electrical polarity of the substrate are crucial, i.e., the transitions only take place at positive substrate bias and elevated temperatures. Molecular mechanics simulations were carried out to calculate the temperature and electric field dependence of the adsorption enthalpy and free energy of the chicken-wire assembly of TMA on the two layers of graphene surface. The calculated decrease in adsorption enthalpy with the increase of temperature and electric field values that causes the TMA chicken-wire assembly to be less stable is proposed to promote the occurrence of the phase transition observed by STM. This study paves the way toward program-controlled supramolecular phase switching via the synergic effect of electrical and thermal stimuli.
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