Ultrafast photophysics of iridium complexes

This thesis presents ultrafast photophysical measurements on a number of phosphorescent iridium complexes and establishes relationships between the relaxation rates and the vibrational properties of the material. When ultrafast luminescence is measured on the peak of the phosphorescence spectrum and on its red-side, 230 fs and 3 ps decay time constants were observed in all materials studied, and this was attributed to population redistribution amongst the three electronic substates of the lowest triplet metal-ligand charge transfer (MLCT) state. The observation of luminescence at higher values of energy embodied ultrafast dissipation of excess energy by intramolecular vibrational redistribution (IVR) and it was found that the dissipation channels and rate of IVR could be modified by chemical modification of the emitting molecule. This was tested in two ways. Firstly by adding electronically inactive dendrons to the core, an increase in the preference for dissipation of excess energy by IVR rather than by picosecond cooling to the solvent molecules was found, but this did not change the rate of IVR. The second method of testing was by fusing a phenyl moiety directly onto the ligand, this both increased the rate of IVR and also the preference for dissipation by it rather than by picosecond cooling. Fluorescence was recorded in an iridium complex for the first time and a decay time constant of 65 fs was found, thus allowing a direct observation of intersystem crossing (ISC) to be made. In a deep red emitting iridium complex internal conversion (IC) and ISC were observed and the factors controlling their time constants deduced. IC was found to occur by dissipation of excess energy by IVR. The rate of IC was found to be dependent on the amount of vibrational energy stored in the molecule, with IC fast (< 45 fs) when < 0.6 eV of energy is stored and slower (~ 70 fs) when the value is > 0.6 eV. The rate of ISC agreed with these findings, indicating that the very process of ISC may be thought of as closely analogous to that of IC given the strongly spin-mixed nature of the singlet and triplet MLCT states