Responsive and dynamic molecular systems are of high interest for a better understanding of natural systems and for the development of next-generation materials. In general, it can be difficult to predict supramolecular packing and self-assembly behavior in dynamic systems because of the delicate balance between intermolecular interactions of varying strength and length scale. We approach this problem through a combination of innovative organic synthesis, molecular-level self-assembly characterization, and multiscale simulation. This work involves close collaboration with other research groups that have expertise in design, synthesis, functional characterization, theory, and computational modeling. This interdisciplinary and collaborative approach has allowed us to develop insight into molecular assembly processes and how those can be tuned to steer organic thin film architecture and function. Here, we will present examples of molecular systems where we have tuned intermolecular interactions to explore different structural phases of assembly. Some of these exhibit dynamic behavior. We also show examples of how that dynamic behavior can be used to create a structural response to chemical and electronic stimuli.