The synthesis and photophysical properties of the complex [Fe(phen)(2)(TTF-dppz)](2+) (TTF-dppz = 4',5'-bis-(propylthio)tetrathiafulvenyl[i]dipyrido[3,2-a:2',3'-c]phenazine, phen = 1,10-phenanthroline) are described. In this complex, excitation into the metal-ligand charge transfer bands results in the population of a high-spin state of iron(II), with a decay lifetime of approximately 1.5 ns, in dichloromethane, at room temperature. An intraligand charge transfer state can also be obtained and has a lifetime of 38 ps. A mechanism for the different states reached is proposed based on transient absorption spectroscopy.