Dissipative supramolecular systems

• Applicant: Dr. Larissa von Krbek-Prömel
• Subject Area: Organic Molecular Chemistry - Synthesis and Characterisation
• Term: since 2020
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 446317932

Most supramoleclar self-assembly processes are thermodynamically driven, i.e. energetically high components assemble into a thermodynamically more favourable structure. In contrast, natural systems predominantly operate far from equilibrium through the dissipation of energy — i.e. their assembly is driven by the consumption of a fuel, allowing for greater structural complexity, spatiotemporal control over function, self-healing, adaptivity, emergent behaviour, and the ability to perform work. Implementing such out-of-equilibrium (OOE) processes into synthetic systems will lead to greater complexity and function in man-made materials and will profoundly impact the fields of chemistry, material science, and synthetic biology. Furthermore, investigation of these man-made out-of-equilibrium systems might provide a better understanding of the kinetic and thermodynamic constraints in living systems. While the field of supramolecular chemistry has taken first steps towards realising dissipative self-assembly (DSA) of gels, polymers, and colloids, smaller supramolecular structures such as metallo-supramolecular cages are still lacking. The aim of this project is to design and investigate new metallo-supramolecular systems that assemble through the dissipation of energy, with the final goal of furthering our understanding of out-of-equilibrium systems and emergent behaviour. The first goal of this project is the synthesis and investigation of new mononuclear metal complexes that assemble far from the thermodynamic equilibrium by energy dissipation — either via a chemical fuel or a light. With a couple of these mononuclear model systems at hand, this project will move on to the second major aim, the challenging dissipative self-assembly of metallo-supramolecular cages. Self-assembly of three-dimensional cages adds a level of complexity to the systems, which makes them more suitable as model compounds to understand dissipative self-assembly in nature. The long-term goals of this project are using the previously established out-of-equilibrium systems to understand emergent behaviour in supramolecular chemistry and possibly in nature and utilise the dynamic behaviour of the out-of-equilibrium cages to tackle common drawbacks of conventional supramolecular chemistry, namely, gaining spatiotemporal control over guest release and circumventing product inhibition in supramolecular catalysis. Confinement of molecular systems into nanospaces (e.g. vesicles) can lead to unprecedented behaviour and possibly emergence.

• DFG Programme: Independent Junior Research Groups
• International Connection: Switzerland
• Cooperation Partners: Professorin Dr. Cornelia Palivan; Professor Dr. Konrad Tiefenbacher