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Intracellular Photophysics of an Osmium Complex bearing an Oligothiophene Extended Ligand
Authors:Kilian R A Schneider  Avinash Chettri  Houston D Cole  Dr Katharina Reglinski  Jannik Brückmann  John A Roque III  Dr Anne Stumper  Dr Djawed Nauroozi  Dr Sylvia Schmid  Dr Christoffer B Lagerholm  Prof Dr Sven Rau  Prof Dr Peter Bäuerle  Prof Dr Christian Eggeling  Dr Colin G Cameron  Prof Dr Sherri A McFarland  Prof Dr Benjamin Dietzek
Institution:1. Department Functional Interfaces (K.R.A.S., A.C., B.D.), Department Biophysical Imaging (K.R., C.E.), Leibniz Institute of Photonic Technology (IPHT) e. V., Albert-Einstein-Straße 9, 07745 Jena, Germany

Institute of Physical Chemistry and Abbe Center of Photonics, Friedrich-Schiller-University Jena, Helmholtzweg 4, 07743 Jena, Germany;2. Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, TX, 76019-0065 USA;3. Department Functional Interfaces (K.R.A.S., A.C., B.D.), Department Biophysical Imaging (K.R., C.E.), Leibniz Institute of Photonic Technology (IPHT) e. V., Albert-Einstein-Straße 9, 07745 Jena, Germany

Institute of Applied Optic and Biophysics, Friedrich-Schiller University Jena, Max-Wien-Platz 1, 07743 Jena, Germany

University Hospital Jena, Bachstraße 18, 07743 Jena, Germany;4. Institute of Inorganic Chemistry I, Ulm University, Albert-Einstein-Allee 11, 89081 Ulm, Germany;5. Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, TX, 76019-0065 USA

Department of Chemistry and Biochemistry, The University of North Carolina at Greensboro, Greensboro, North Carolina, 27402 USA;6. Institute of Organic Chemistry II and Advanced Materials, Ulm University, Albert-Einstein-Allee 11, 89081 Ulm, Germany;7. <8. MRC Human Immunology Unit & Wolfson Imaging Center Oxford, Headley Way, Oxford, OX3 9DS UK;9. Department Functional Interfaces (K.R.A.S., A.C., B.D.), Department Biophysical Imaging (K.R., C.E.), Leibniz Institute of Photonic Technology (IPHT) e. V., Albert-Einstein-Straße 9, 07745 Jena, Germany

Institute of Applied Optic and Biophysics, Friedrich-Schiller University Jena, Max-Wien-Platz 1, 07743 Jena, Germany

<10. Department Functional Interfaces (K.R.A.S., A.C., B.D.), Department Biophysical Imaging (K.R., C.E.), Leibniz Institute of Photonic Technology (IPHT) e. V., Albert-Einstein-Straße 9, 07745 Jena, Germany

Abstract: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)](PF6)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}imidazo4,5-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 3ILCT 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.
Keywords:in vitro spectroscopy  oligothiophene  osmium polypyridyl  transient absorption  ultrafast spectroscopy
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