AcetylacetonateBODIPY-Biscyclometalated Iridium(III) Complexes: Effective Strategy towards Smarter Fluorescent Photosensitizer Agents

Abstract

Biscyclometalated IrIII complexes involving boron-dipyrromethene (BODIPY)-based ancillary ligands, where the BODIPY unit is grafted to different chelating cores (acetylacetonate for Ir-1 and Ir-2, and bipyridine for Ir-3) by the BODIPY meso position, have been synthesized and characterized. Complexes with the BODIPY moiety directly grafted to acetylacetonate (Ir-1 and Ir-2) exhibit higher absorption coefficients (ϵ≈4.46×104 m−1 cm−1 and 3.38×104 m−1 cm−1 at 517 nm and 594 nm, respectively), higher moderate fluorescence emission (φfl≈0.08 and 0.22 at 528 nm and 652 nm, respectively) and, in particular, more efficient singlet oxygen generation upon visible-light irradiation (φΔ≈0.86 and 0.59, respectively) than that exhibited by Ir-3 (φΔ≈0.51, but only under UV light). Phosphorescence emission, nanosecond time-resolved transient absorption, and DFT calculations suggest that BODIPY-localized long-lived 3IL states are populated for Ir-1 and Ir-2. In vitro photodynamic therapy (PDT) activity studied for Ir-1 and Ir-2 in HeLa cells shows that such complexes are efficiently internalized into the cells, exhibiting low dark- and high photocytoxicity, even at significantly low complex concentration, making them potentially suitable as theranostic agents. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim