Picosecond measurements of optical nonlinearities in King's complex and synthesized analogues

We have measured the photodynamics of reverse saturable absorption (RSA) in solutions of cyclopentadienyliron carbonyl tetramer (King's complex) using picosecond pump-probe techniques. Similar preliminary measurements in solutions of synthesized variations of the King's complex indicate that the excited state transition responsible for the observed RSA is most likely a second d-d transition within the metal core of the molecule. On time scales of hundreds of picoseconds, the observed RSA in the King's complex is well characterized by a three-level rate-equation, singlet-state absorption model, where the excited-state cross section is greater than that of the ground state. On nanosecond timescales and at fluences above 200 mJ.cm^-2, however, we observe the onset of a response that is consistent with a thermally induced scattering process. Further evidence of this scattering is provided by angularly-resolved measurements of the transmitted and back-scattered signals for nanosecond excitation. When the King's complex is incorporated in a solid host negligible scatter was observed and the response is completely described by the singlet parameters extracted from the picosecond measurements. The observation of, scatter from solution, together with a time-resolved decay to the ground state that is rapid (∼120 ps) and largely nonradiative in this molecule, indicate that solutions of King's complex may provide a mechanism for efficiently generating thermal nonlinearities on a subnanosecond timescale.