An unusual iridium complex, [(dfpbo)(2)Ir](2) [dfpbo = 2-(3,5-difluorophenyl)benzoxazolato-N,C-2'], which is the first dimeric iridium complex composed of two bis-cyclometalated Ir-II structures connected by an unsupported Ir-II-Ir-II bond, has been synthesized and fully characterized. Under mild conditions of neutral pH at room temperature, this complex dissociated spontaneously to form the stable radical [Ir(dfpbo)(2)](center dot),