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 18 pi aromatic tetrapyrrole macrocyclic skeleton containing a tri-fused pentacyclic moiety. Here, the synthesis of an iridium complex of N-fused bilatrienone is reported 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 pi-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 (kappa(1),eta(3)-C8H12)-Ir complex.