A series of cyclometalated iridium(iii) complexes [Ir(C^N)2(N^N)][PF6] (N^N = 2,2′-bipyridine (1), 6-phenyl-2,2′-bipyridine (2), 4,4′-di-tert-butyl-2,2′-bipyridine (3), 4,4′-di-tert-butyl-6-phenyl-2,2′-bipyridine (4); HC^N = 2-(3-phenyl)phenylpyridine (HPhppy) or 2-(3,5-diphenyl)phenylpyridine (HPh2ppy)) are reported. They have been synthesized using solvento precursors so as to avoid the use of chlorido-dimer intermediates, chloride ion contaminant being detrimental to the performance of [Ir(C^N)2(N^N)][PF6] emitters in light-electrochemical cell (LEC) devices. Single crystal structure determinations and variable temperature solution 1H NMR spectroscopic data confirm that the pendant phenyl domains engage in multiple face-to-face π-interactions within the coordination sphere of the iridium(iii) centre. The series of [Ir(Phppy)2(N^N)]+ and [Ir(Ph2ppy)2(N^N)]+ complexes investigated include those with and without intra-cation face-to-face π-stacking. All the complexes display excellent luminescent properties, in particular when employed in thin solid films. The most important observation is that all the LECs using the [Ir(Phppy)2(N^N)]+ and [Ir(Ph2ppy)2(N^N)]+ emitters (i.e. with and without intra-cation π-stacking interactions) exhibit very stable luminance outputs over time, even when driven at elevated current densities. The most stable LEC had an extrapolated lifetime of more than 2500 hours under accelerated testing conditions.