Tuning solid state luminescent properties in a hydrogen bonding-directed supramolecular assembly of bis-cyclometalated iridium(iii) ethylenediamine complexesElectronic supplementary information (ESI) available. CCDC reference numbers 850263850268. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c2dt12108e

Synthesis, crystal structural determination and photophysical properties of a series of heteroleptic cationic cyclometalated iridium( iii ) derivatives of general formula [(ppy) 2 Ir(en)]X (X = ClO 4 ( 1 ), PF 6 ( 2 ), Cl ( 3 ), BPh 4 ( 4 )), are described. The assembly of the common molecular building block allows to get highly luminescent crystalline materials or to assemble poorly luminescent supramolecular channelled architectures, 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 specific crystalline 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 highly luminescent materials. Engineering hydrogen-bonded supramolecular materials based on iridium( iii ) complex cations with tunable photophysical properties in the solid state.