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Unconventionally modified dibenzoylmethane (dbm) ligands have been synthesized and successfully utilized as ancillary ligands for neutral iridium(III) complexes of the formula [Ir(dFppy)2(LX)], where dFppyH is 2‐(2,4‐difluorophenyl)pyridine and LX is tribenzoylmethane (tbm) or 1‐phenyl‐3‐(4‐(pyridin‐2‐yl)phenyl)propane‐1,3‐dione (pydbm). The modification of the ligands aims to prevent or enhance possible intermolecular interactions between the dFppy and/or the LX moiety in comparison with the previously reported [Ir(dFppy)2(dbm)] complex. The aggregation induced emission (AIE) properties of these complexes are significantly modulated, as a consequence of the different π–π interactions revealed by X‐ray crystallography. The structural and photophysical properties of neutral iridium(III) complexes using modified β‐diketonates as ancillary ligands have been investigated, resulting in significantly modulated aggregation induced emission properties. [ABSTRACT FROM AUTHOR]

The Front Cover shows the two Ir complexes bearing β‐diketone/triketonate ligands. Upon UV light irradiation in the solid state, both molecules show visible emission ranging from yellow to red. This emission is negligible in solution, confirming that these compounds are aggregation‐induced emitters (AIE). The molecular packing in the crystal and the alteration of the π–π stacking involving the ancillary ligands determines the nature of the emission. The importance of structural parameters in comprehending the solid‐state phosphorescence of Ir complexes is highlighted by merging the experimental solid‐state emissions and crystal structures of the complexes. More information can be found in the Full Paper by D. Jacquemin, M. I. Ogden, M. Massi, E. Zysman‐Colman et al. For more on the story behind the cover research, see the Cover Profile. [ABSTRACT FROM AUTHOR]