10‐Silacorroles Exhibiting Near‐Infrared Absorption and Emission

10‐Silacorroles were obtained from the Pd‐catalyzed silylative cyclization of a bis(α,α′‐dibromodipyrrin) NiII precursor with dihydrosilanes. These 10‐silacorroles show substantially red‐shifted absorption bands relative to those of normal porphyrins and isocorroles. Notably, the corresponding free base and ZnII 10‐silacorroles exhibit emissions in the NIR region. Theoretical calculations on these 10‐silacorroles revealed the presence of σ*–π* conjugation between the silyl group and the tetrapyrrole π system, which significantly lowers their LUMO energy levels. Jump to 1000 nm! A new family of heteroporphyrinoid, 10‐silacorroles, has been prepared through Pd‐catalyzed silylation of a dibromodipyrrin NiII precursor. 10‐Silacorroles exhibited near‐infrared absorption (NIR) and emission. Theoretical analysis and electrochemical investigation revealed the presence of σ*–π* conjugation between the silicon atom and tetrapyrrolic macrocyclic skeleton.