Pseudorotaxane strategies for guiding self-assembly and the application of molecular machinery in photoelectrochemical devices

Over the years, chemists have become masters of covalent bond formation, demonstrated by the ability to synthesize complicated natural products and their derivatives. Conversely, control of structures beyond the molecule has not yet reached the same level of sophistication. Supramolecular organization is ubiquitous in biology and non-covalent interactions are extensively applied to (pre-)organize the individual compositional elements to achieve optimal operation as emergent functionality. Understanding (supra)molecular organization could enable the creation of novel types chemical systems with new functions. This thesis aims to explore the use of supramolecular organization by using pseudorotaxane strategies to create functional chemical systems. As both fundamental understanding and application are investigated in this thesis, the work is divided into two parts.
Part A demonstrates two examples of pathway engineering for non-covalent synthesis by employing a pseudorotaxane strategy. In one example the ring is used as a catalyst to guide self-assembly, while in the second example the ring binding impedes on the possible outcomes of multi-ligand architectures, and thereby organizing the self-assembled structures.
In part B the central topic is supramolecular organization to improve charge separation in artificial photosynthesis. Photoelectrochemical devices benefit from implementing supramolecular organization promoting the forward electron propagation, eventually leading to enhanced device performance. Using this bio-inspired approach, three different types of molecular machines were designed and applied to address electron-hole recombination issues found in p-DSSCs.
In both parts of the thesis, the power of the non-covalent bond is demonstrated, gaining insight in possible applications and underlying concepts of chemistry beyond the molecule.