Visible-Light-Driven Triplet Sensitization of Polycyclic Aromatic Hydrocarbons Using Thionated Perinones

Metal-free chromophores that efficiently generate triplet excited states represent enticing alternatives with respect to transition metal-containing photosensitizers, such as those featuring metal-to-ligand charge transfer excited states. Yet, such molecular constructs have remained underexplored due to the unclear relationship(s) between molecular structure and efficient/rapid intersystem crossing. In this regard, we present a series of three thionated perinone chromophores serving as a newly conceived class of heavy metal-free triplet photosensitizers. We demonstrate that thionation of the lone C=O substituent in each highly fluorescent perinone imparts red-shifted absorbance bands that maintain intense extinction coefficients across the visible spectrum, as well as unusually efficient triplet excited state formation as inferred from the measured singlet O₂ quantum yields at 1270 nm (Φ_Δ = 0.78–1.0). Electronic structure calculations revealed the emergence of a low energy S₁ (n → π*) excited state in the proximity of a slightly higher energy S₂ (π → π*) excited state. The distinct character in each of the two lowest-lying singlet state manifolds resulted in the energetic inversion of the corresponding triplet excited states due to differences in electron exchange interactions. Rapid S₁ → T₁ intersystem crossing was thereby facilitated in this manner through spin–orbit coupling as predicted by the El Sayed rules. The lifetimes of the resultant triplet excited states persisted into the microsecond time regime, as measured by transient absorbance spectroscopy, enabling effective bimolecular triplet sensitization of some common polycyclic aromatic hydrocarbons. The synthetically facile interchange of a single O atom to an S atom in the investigated perinones resulted in marked changes to their photophysical properties, namely, conversion of dominant singlet state fluorescence in the former to long-lived . Authors: Palmer, Jonathan R. [North Carolina State Univ., Raleigh, NC (United States); NC State University]; Wells, Kaylee A. [North Carolina State Univ., Raleigh, NC (United States)] (ORCID:0000000268706574); Yarnell, James E. [North Carolina State Univ., Raleigh, NC (United States); United States Air Force Academy, Colorado Springs, CO (United States)] (ORCID:0000000300499887); Favale, Joseph M. [North Carolina State Univ., Raleigh, NC (United States)]; Castellano, Felix N. [North Carolina State Univ., Raleigh, NC (United States)] (ORCID:0000000175468618). DOE Contract: SC0011979. Subjects: 14 SOLAR ENERGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY