Mixed‐Valence Tetrametallic Iridium Chains

Abstract

AbstractNeutral [X−{Ir2}−{Ir2}−X] (X=Cl, Br, SCN, I) and dicationic [L−{Ir2}−{Ir2}−L]2+ (L=MeCN, Me2CO) tetrametallic iridium chains made by connecting two dinuclear {Ir2} units ({Ir2}=[Ir2(μ‐OPy)2(CO)4], OPy=2‐pyridonate) by an iridium–iridium bond are described. The complexes exhibit fractional averaged oxidation states of +1.5 and electronic delocalization along the metallic chain. While the axial ligands do not significantly affect the metal–metal bond lengths, the metallic chain has a significant impact on the iridium–L/X bond distances. The complexes show free rotation around the unsupported iridium‐iridium bond in solution, with a low‐energy transition state for the chloride chain. The absorption spectra of these complexes show characteristic bands at 438–504 nm, which can be fine‐tuned by varying the terminal capping ligands.