Probing the excited state properties of the highly phosphorescent Pt(dpyb)Cl compound by high-resolution optical...

Detailed photophysical studies of the emitting triplet state of the highly phosphorescent compound Pt(dpyb)Cl based on high-resolution optical spectroscopy at cryogenic temperatures are presented {dpyb = N--C(2)--N-coordinated 1,3-di(pyridylbenzene)}. The results reveal a total zero-field splitting of the emitting triplet state T(1) of 10 cm(-1) and relatively short individual decay times for the two higher lying T(1) substates II and III, while the decay time of the lowest substate I is distinctly longer. Further evidence for the assignment of the T(1) substates is gained by emission measurements under high magnetic fields. Distinct differences are observed in the vibrational satellite structures of the emissions from the substates I and II, which are dominated by Herzberg-Teller and Franck-Condon activity, respectively. At T = 1.2 K, the individual spectra of these two substates can be separated by time-resolved spectroscopy. For the most prominent Franck-Condon active modes, Huang-Rhys parameters of S approximately 0.1 can be determined, which are characteristic of very small geometry rearrangements between the singlet ground state and the triplet state T(1). The similar geometries are ascribed to the high rigidity of the Pt(N--C--N) system which, unlike complexes incorporating bidentate phenylpyridine-type ligands and exhibiting similar metal-to-ligand charge transfer admixtures, cannot readily distort from planarity. The results provide new insight into strategies for optimizing the performance of platinum-based emitters for applications such as organic light-emitting diode (OLED) technology and imaging.