Metal‐Bridging Cyclic Bilatriene Analogue Affords Stable π‐Radicaloid Dyes with Near‐Infrared II Absorption

Stable neutral metal radicaloid complexes have been synthesized from a modified tetrapyrrolic pigment, bilatriene, with iridium(I) and rhodium(I) cyclooctadiene (COD) synthons. The bilatriene skeleton contains α-linked conjugated pyrrole units, whereas an N-confused analogue used in this work possesses β-linked pyrrole moieties at the terminal, demonstrating a unique metal binding capability. Unprecedentedly, the metal-COD cations are accommodated at the outer nitrogen sites, which induced the formation of open-shell metal-radicaloid species. The resulting compounds are highly stable under ambient conditions and demonstrated facile redox conversion to afford the corresponding cation and anion species. Furthermore, the radicaloid complexes showed a distinct second near-infrared absorption (NIR-II) capability extending up to 1500 nm along with high photostability. These features emphasized that the complexes can be potential NIR-II light-responsible photothermal and photoacoustic imaging contrast agents based on the metal-radicaloid dye platform.