Reactions of [Ir(C^N)(2)Cl](2) [HC^N = 2-(3-R-phenyl)pyridine, 2-(3-R-phenylpyrazole) R = H, Me] with Me(2)-phencat give luminescent complexes [Ir(C^N)(2)(Me(2)-phencat)][PF(6)] (Me(2)-2a, b, c)[PF(6)]. Deprotection of the methoxy groups with BBr(3) is problematic as simultaneous bromination of the cyclometallated phenyl groups occurs. However, deprotection of Me(2)-phencat with BBr(3) followed by complexation with [Ir(C^N)(2)Cl](2) gives luminescent complexes [Ir(C^N)(2)(H(2)-phencat)][PF(6)] (H(2)-3a, c)[PF(6)], which are luminescent sensors for molybdate.