Synthesis of transition metal complexes with strong absorption in the near-infrared (NIR) region of the visible spectra has been a long term goal among inorganic chemists for their potential as low-energy photosensitizers. Previously in our lab, the investigation of heteroleptic ruthenium(II) photosensitizers with “non-innocent” oxy- and amido-quinolate ligands demonstrated their excellent redox tunability and enhanced absorption properties towards photovoltaic applications. This “non-innocent ligand” effect involves the tailored design of hybrid metal(<i>d</i>p)-ligand(p) frontier molecular orbitals that precludes formal assignment of the central metal oxidation state. Incorporating this design strategy opens a new and exciting avenue of exploration for the design of NIR absorbing transition metal based photosensitizers with potential solar energy conversion and phototherapeutic applications. The electronic and photophysical properties for a series of ruthenium(II) and iridium(III) photosensitizers will be presented where the diversity of 8-oxyquinolate ligands is explored through design variation of the addition of a  merocyanine acceptor. A combination of computational, UV-Vis absorption and cyclic voltammetry studies will be used to assess the influence of these ligands on complex electronic and photophysical properties. Photovoltaic device characterization will also be presented including power conversion efficiency, incident photon-to-current conversion efficiency and electrochemical impedance spectroscopy.

NIR absorbance of Ru(II) and Ir(III) photosensitizers containing a merocyanine π-acceptor

254th National Meeting (2017)

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