Stable Monometallic Ir(I) Complexes of Porphycene through β,β′-Bipyrrole Fusion

Iridium complexation was investigated for β-tetraisopropyldinaphthoporphycene. Usage of 1,5-cyclooctadiene and dimethylformamide separately as solvents led to the formation of a Ir(I) complex with 1,5-cyclooctadiene (COD) as a secondary ligand and an additional complex where COD is oxidized. These are the first examples of complexes of porphycene or its isomers, where in-core iridium is stabilized in a 1+ oxidation state without any carbonyl ligands. The latter complex was found to be stable under aerobic conditions at elevated temperature. The synthesis, characterization, and photophysical and electrochemical properties of the Ir(I) complexes are elaborated on here.