Material Profiling for Photocrystallography: Relating Single-Crystal Photophysical and Structural Properties of Luminescent Bis-Cyclometalated Iridium-Based Complexes

Abstract

The photophysical properties of seven luminescent iridium complexes are characterized in their single-crystal form, and the photoactivity is related to their molecular structures. Specifically, solid-state optical emission spectra and associated lifetimes are determined from single crystals of iridium complexes containing three bidentate ligands: two variously substituted 2-phenylbenzothiazoles and either a 2,4-pentadione (acetylacetone) or 2-pyridinecarboxylic (picolinic) acid. All complexes studied exhibit emissive behavior in the solid-state which originates from 3π–π* and metal-to-ligand-charge-transfer (MLCT) electronic transitions; this is supported by density functional theory. Phosphorescence is observed in all cases with microsecond lifetimes, ranging from 0.30 to 2.4 μs at 298 K and 1.4–4.0 μs at 100 K. Structure–property relationships are established which are relevant to the potential solid-state application of this series of luminescent complexes as organic light emitting diodes (OLED) material components. In addition, these materials are assessed for their suitability to time-resolved pump–probe photocrystallography experiments, which will reveal their photoexcited state structure. Accordingly, the design process by which materials are selected and technical parameters are defined for a photocrystallography experiment is illustrated. This family of complexes presents a case study for this photocrystallography material profiling. Results show that the time-resolved photoexcited state structure, featuring the MLCT transition is, in principle at least, viable for two of these complexes.