Reaction of bis(peri-substituted) triphosphine iPrP(AcenapPiPr2)2 (Acenap = acenaphthene-5,6-diyl) with iodine, followed by hydrolysis, afforded ionic species [iPrP(AcenapP(O)iPr2)2] dication, containing P-O-P-O-P motif, balanced triiodide anions. The new were fully characterised, including single crystal X-ray diffraction. formation the unusual double-bridged motif is likely a result crowding ...