Mixing Behavior of Trimesic Acid with Pentacene at the Liquid–Solid Interface

• Published in: Journal of physical chemistry. C Vol. 124; no. 41; pp. 22521 - 22528
• Main Authors: Zeng, Xingming, Mahmood, Ayyaz, Guo, Jiangtao, Hu, Yi, Chan, Yue, Lee, Shern-Long
• Format: Journal Article
• Language: English
• Published: American Chemical Society 15-10-2020
• Subjects: C: Surfaces, Interfaces, Porous Materials, and Catalysis
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/acs.jpcc.0c06891

The self-assembly of organic molecules on a solid surface presents a promising route toward the nanoscale-precision construction of functional patterns. In particular, using trimesic acid (TMA) and its self-assembled networks, here we report a template-assisted method to engineer well-ordered structures of pentacene at the organic solvent–graphite interface. Scanning tunneling microscopy revealed that pentacene molecules were merely adsorbed into the TMA chicken-wire (CW) polymorph, and in turn, the template underwent certain rearrangements, leading to more specific selectivity in the form of cocrystallization. Moreover, molecular mechanics and density functional theory simulations of the adsorption energy and the additional stabilizing energy, induced by hydrogen bonds during assembly formations, provide insights into the relative stability of different assembled structures. The calculated larger negative entropy change in the TMA flower polymorph results in the smaller change in Gibbs free energy during the assembling processes, compared with the CW structure, leading to the majority of the higher-stability hybrid structure after a long time run.