Synthesis, Emission Characteristics, Cellular Studies, and Bioconjugation Properties of Luminescent Rhenium(I) Polypyridine Complexes with a Fluorous Pendant

In this article, we report the photophysical and biological properties of new luminescent rhenium(I) polypyridine fluorous complexes. The complexes [Re(N∧N)(CO)3(py-Rf-NH2)](PF6) (py-Rf-NH2 = 3-amino-5-(N-((3-perfluorooctyl)propyl)aminocarbonyl)pyridine; N∧N = 1,10-phenanthroline (phen) (1a), 3,4,7,8-tetramethyl-1,10-phenanthroline (Me4-phen) (2a), 4,7-diphenyl-1,10-phenanthroline (Ph2-phen) (3a)) contain a fluorous pendant and a primary amine for modification. They have been converted to the isothiocyanate complexes [Re(N∧N)(CO)3(py-Rf-NCS)](PF6) (py-Rf-NCS = 3-isothiocyanato-5-(N-((3-perfluorooctyl)propyl)aminocarbonyl)pyridine; N∧N = phen (1b), Me4-phen (2b), Ph2-phen (3b)) with thiophosgene. The isothiocyanate complexes have been reacted with ethylamine, a model substrate, yielding the thiourea complexes [Re(N∧N)(CO)3(py-Rf-TU-Et)](PF6) (py-Rf-TU-Et = 3-ethylthioureidyl-5-(N-((3-perfluorooctyl)propyl)aminocarbonyl)pyridine; N∧N = phen (1c), Me4-phen (2c), Ph2-phen (3c)). Upon irradiation, all of these...