Modular, Self-Assembling Metallaphotocatalyst for Cross-Couplings Using the Full Visible-Light Spectrum

The combination of nickel and photocatalysis has unlocked a variety of cross-couplings. These protocols rely on a few photocatalysts that can only convert a small portion of visible light (<500 nm) into chemical energy. The high-energy photons that excite the photocatalyst can result in unwanted side reactions. Dyes that absorb a much broader spectrum of light are not applicable because of their short-lived singlet excited states. Here, we describe a self-assembling catalyst system that overcomes this limitation. Immobilization of a nickel catalyst on dye-sensitized titanium dioxide results in a material that catalyzes carbon–heteroatom and carbon–carbon bond formations. The modular approach of dye-sensitized metallaphotocatalysts accesses the entire visible light spectrum and allows tackling selectivity issues resulting from low wavelengths strategically. The concept overcomes current limitations of metallaphotocatalysis by unlocking the potential of dyes that were previously unsuitable.