Abstract
Supramolecular assemblies are ubiquitous in biological systems and often regulate vital complex cellular tasks. Nature has mastered the ability to engineer sophisticated hierarchical assemblies with emergent behaviors and structure-function properties. Supramolecular chemistry, drawing inspiration from the complex assemblies in biological systems, attempts to mimic nature's proficiency in creating complex materials through noncovalent interactions. This field has significantly advanced the past two decades, offering a plethora of supramolecular systems that can self-organize into tailored architectures under thermodynamic control. Yet, biological functionalities often emerge from configurations that transcend these global energy minima, venturing into non-equilibrium states where kinetic traps and metastable assemblies exist. Recent decades have seen a concerted effort to navigate the potential energy landscape with molecular precision, enabling the reconfiguration of building blocks from equilibrium to dynamic, nonequilibrium states. This exploration has been pivotal in developing materials that exhibit emergent behaviors akin to those found in living systems, which constantly consume energy to maintain non-equilibrium states. Amongst the numerous building blocks capable of self-assembly, π-conjugated chromophores stand out for their capacity to transfer energy and conduct electricity when doped, showcasing the potential for creating materials that respond dynamically to environmental stimuli. This thesis leverages such building blocks, focusing on naphthalene diamide and porphyrin systems, to generate supramolecular systems with manipulable structure-function properties in different thermodynamic states.