Dual-catalytic architectures accommodated by titanium-oxo clusters boosting visible-light-driven C-N cross-coupling...

Area of Science:

• Materials Science
• Catalysis
• Photochemistry

Background:

• Dual-catalytic systems integrating photoactive and transition metal sites are promising for light-driven cross-coupling.
• Surface engineering of clusters offers a novel approach to catalyst design.

Purpose of the Study:

• To develop synergistic dual-catalytic architectures based on surface-engineered Ti6-oxo clusters.
• To achieve efficient photocatalytic formation of C-N bonds using these novel architectures.

Main Methods:

• Ti6-oxo clusters were decorated with bipyridine ligands via competitive coordination.
• Iridium photo-sensitizers and nickel catalytic centers were anchored to electron-rich nitrogen sites.
• The resulting Ni-Ir/Ti6-Bpca system was characterized for its catalytic performance.

Main Results:

• The Ni-Ir/Ti6-Bpca system demonstrated significantly enhanced charge transfer efficiency through intramolecular electron transfer.
• The catalyst exhibited boosted catalytic activity across diverse substrates with remarkable functional group tolerance.
• Suppression of metal site leaching and nickel black formation was observed due to coordination protection.

Conclusions:

• The developed Ni-Ir/Ti6-Bpca system provides a blueprint for sustainable cross-coupling methodologies.
• This work highlights the potential of titanium-oxo clusters in photocatalysis, offering enhanced electron transfer kinetics and operational stability.