Temperature-Induced Nanoarchitectonics of Monolayer Self-Assembly of Heterocoronene-Based Discotic Liquid Crystals

Enhancing molecular self-assembly at the monolayer level offers significant potential for various applications. For monolayers made of π-conjugated discotic liquid crystal (DLC) molecule nanowires, achieving precise separation and alignment of these nanowires has been a long-standing challenge. This research explores an approach using the manipulation of subphase temperature and surface pressure within a Langmuir trough to control molecular nanowire separation. We observe notable temperature-dependent behavior: as the temperature increases from 5 to 30 °C, the monolayer collapse pressure rises steadily. In contrast, temperatures from 35 to 50 °C exhibit an initial small plateau with a nonzero slope that becomes more distinct with rising temperature. Our study of Langmuir-Blodgett (LB) films provides crucial insights into the monolayer's structure. At lower temperatures, the LB films show coalesced molecular nanowires, whereas at higher temperatures, the DLC nanowires separate and form an interconnected network. Remarkably, upon compression, this network transforms into a compact, highly uniform monolayer. To explain these temperature-dependent behaviors, we examine the area relaxation curves, which indicate a two-step molecular loss mechanism involving desorption and monolayer collapse due to the nucleation and growth of critical nuclei. This extensive study offers valuable insights into the dynamic interaction of the temperature, surface pressure, and molecular assembly, enhancing our understanding of the fundamental processes in monolayer self-assembly.