Intracellular photophysics of an osmium complex bearing an oligothiophene extended ligand

This contribution describes the excited‐state properties of an Osmium‐complex when taken up into human cells. The complex 1 [Os(bpy) 2 (IP‐4T)](PF 6 ) 2 with bpy=2,2′‐bipyridine and IP‐4T=2‐{5′‐[3′,4′‐diethyl‐(2,2′‐bithien‐5‐yl)]‐3,4‐diethyl‐2,2′‐bithiophene}imidazo[4,5‐ f ][1,10]phenanthroline) can be discussed as a candidate for photodynamic therapy in the biological red/NIR window. The complex is taken up by MCF7 cells and localizes rather homogeneously within in the cytoplasm. To detail the sub‐ns photophysics of 1 , comparative transient absorption measurements were carried out in different solvents to derive a model of the photoinduced processes. Key to rationalize the excited‐state relaxation is a long‐lived 3 ILCT state associated with the oligothiophene chain. This model was then tested with the complex internalized into MCF7 cells, since the intracellular environment has long been suspected to take big influence on the excited state properties. In our study of 1 in cells, we were able to show that, though the overall model remained the same, the excited‐state dynamics are affected strongly by the intracellular environment. Our study represents the first in depth correlation towards ex‐vivo and in vivo ultrafast spectroscopy for a possible photodrug.Intracellular excited‐state properties of a photodynamic active Osmium‐complex are investigated. The key to the excited‐state relaxation is the interplay of 3 MLCT and 3 ILCT states on the oligothiophene‐substituted ligand. We successfully tested the model derived from solution with the complex internalized in cells to bridge the gap between cuvette and in vivo measurements for the first time. imag