Iridium Complex of N-Fused Bilatrienone: Oxidative Cleavage of N-Fused Porphyrin Induced by Iridium-Cyclooctadiene Complexation.

N-fused porphyrin (NFP) is a unique class of photostable near-infrared dyes with an 18π aromatic tetrapyrrole macrocyclic skeleton containing a tri-fused pentacyclic moiety. Here we report the synthesis of an iridium complex of N-fused bilatrienone as the degradation product of Ir-cyclooctadiene (cod)-induced oxidative cleavage of NFP under aerobic conditions. Similar to the native bilin chromophores, the ring-opened complex featured a broken π-conjugation circuit and exhibited a broad visible absorption band. In contrast, metalation of NFP using an iridium(I)(cod) complex under an inert atmosphere resulted in the formation of a cod-isomerized ( κ 1 , η 3 -C 8 H 12 )-Ir complex.