Iridium Complex of N‐Fused Bilatrienone: Oxidative Cleavage of N‐Fused Porphyrin Induced by Iridium‐Cyclooctadiene Complexation. Issue 32 (6th May 2021)

• Record Type: Journal Article
• Authors: Abraham, Jibin Alex; Mori, Shigeki; Ishida, Masatoshi; Furuta, Hiroyuki
• Is Part Of: Chemistry. Volume 27:Issue 32(2021)
• Page Start: 8268
• Page End: 8272
• Publication Date: 2021-05-06
• Subjects: cyclooctadiene -- iridium -- NIR absorption -- oxidation -- porphyrin analog; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202100789
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: 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, 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 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 ‐C8 H12 )‐Ir complex. Abstract : Metalation ‐assisted oxidative degradation : Reaction of N‐fused porphyrin with iridium‐cyclooctadiene under aerobic conditions yielded a unique ring‐opened N‐fused bilatrienone analog. The resulting species was isolated as an octahedral iridium complex with significantly modified optical and electrochemical properties.