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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-ligandcharge- 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 timeresolved photoexcited state structure, featuring the MLCT transition is, in principle at least, viable for two of these complexes

crystal growth and design

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