From Molecular to Polymeric Donors: Prolonged Charge Separation in Modular Photoredox-Active Ru(II) Polypyridyl-Type Triads.

In this contribution, the divergent modular synthesis of photoredox-active dyads, triads and a tetrad descending from one ligand precursor is presented by combining "chemistry-on-the-ligand", stepwise complexation and "chemistry-on-the-complex" with minimal synthetic efforts. In the final step, Pd-mediated borylation and subsequent Suzuki-Miyaura cross-coupling was employed to introduce the different (multi)donor moieties at the preassembled P-A dyad subunit. The (spectro-)electrochemical data revealed preserved redox properties of the subunits and minimal driving force for oxidative quenching by the naphthalene diimide-based (NDI) acceptor and, thus, high-energy charge separated (CS) states.

Exploiting Orthogonal C-C Cross-Coupling Reactions for Chemistry-on-the-Complex: Modular Assembly of 2,6-Di(quinolin-8-yl)pyridine Ruthenium(II) Photosensitizer Triads.

In this work, we present a concise modular assembly strategy using one universal heteroleptic 2,6-di(quinolin-8-yl)pyridine-based ruthenium(II) complex as a starting building block. Extending the concept from established ligand modifications and subsequent complexation (), the later appearing chemistry-on-the-complex methodology was used for late-stage syntheses, , assembling discrete building blocks to molecular architectures (here: dyad and triads). We focused on Suzuki-Miyaura and Sonogashira cross-couplings as two of the best-known C-C bond forming reactions.