Encumbering the Copper(I)-Diimine Coordination Sphere with a Benzyl Group: Impact on the Stability and Photoredox Properties

Cu(I)-bisdiimine complexes, [Cu(NN)₂]⁺ (where NN represents a diimine such as phenanthroline or bipyridine derivatives), are considered promising photosensitizers for various photochemical applications. However, their effectiveness is subject to several key challenges. In particular, controlling steric strain around the copper(I) center by introducing appropriate substituents (R) at the α-position of the nitrogen atoms is crucial for optimizing the excited-state properties of the complex. In brief, increasing the size of R leads to longer emission lifetimes and higher quantum yields. Additionally, the energy of the singlet excited state rises with increasing steric bulk, enhancing photoinduced reactivity. However, excessive steric strain from bulky substituents can significantly destabilize the coordination sphere. To balance complex stability with increased steric bulk around the metal center, we have developed two novel nonsymmetrical ligands featuring branched alkyl chains and benzyl groups at the α-position of the nitrogen atoms. Our findings demonstrate that intramolecular π-stacking interactions between the benzyl group and the opposing phenanthroline ligand contribute to stabilizing the coordination sphere. Furthermore, the flexibility of the benzyl group reinforces the tetrahedral geometry around copper(I), resulting in an increased singlet excited-state energy compared to benchmark complexes. Notably, we show that this enhancement in excited-state energy translates into greater excited-state reactivity.