Empirical rules of molecular photophysics in the light of ultrafast spectroscopy

The advent of ultrafast laser spectroscopy has allowed entirely new possibilities for the investigation of the ultrafast photophysics of inorganic metal-based molecular complexes. In this review we show different regimes where non-Kasha behavior shows up. We also demonstrate that while ultrafast intersystem crossing is a common observation in metal complexes, the ISC rates do not scale with the magnitude of the spin-orbit coupling constant. Structural dynamics and density of states play a crucial role in such ultrafast ISC processes, which are not limited to molecules containing heavy atoms.