This Doctoral Thesis demonstrates the potential of supramolecular and anion‑induced redox interactions as effective tools to endow transition metal pincer complexes with adaptive and reversible control over their electronic properties, and consequently over their catalytic behaviour. Systematic studies on Rh(I), Mn(I), and Pd(II) platforms revealed that these interactions can independently modulate the electronic structure and reactivity in a controlled and reversible manner.
The incorporation of the NDI moiety transforms the pincer ligand into a multistimuli-responsive unit that mediates communication between external additives—such as halides and polycyclic aromatic hydrocarbons—and the electronic state of the metal centre. This strategy moves beyond static ligand design and introduces a dynamic approach to catalyst tuning, enabling reversible switching between distinct activity states using mild and easily accessible stimuli. Overall, the study highlights supramolecular and redox-active ligand frameworks as versatile platforms for developing next-generation stimulus-responsive catalysts.
