Tuning Solid State Luminescent Properties in Hydrogen Bonding-Directed Supramolecular Assembly of Bis-Cyclometalated Iridium(III) Ethylenediamine Complexes

Synthesis, crystal structural determination and photophysical properties of a series of heteroleptic cationiccyclometalated iridium(III) derivatives of general formula [(ppy)2Ir(en)]X (X = ClO4− (1), PF6− (2), Cl−(3), BPh4− (4)), are described. The assembly of the common molecular building block allows to gethighly luminescent crystalline materials or to assemble poorly luminescent supramolecular channelledarchitectures, for which the additional contribution of oxygen quenching effects has been observed.Moreover, the high reproducibility of the preparations of the crystalline materials in their specificcrystalline phases, makes the control of the supramolecular organization of photo-active iridium(III)complexes within the crystalline structures a useful synthetic procedure for the construction of highlyluminescent materials.