Triplet Formation and Triplet‐Triplet Annihilation Upconversion in Iodine Substituted Non‐Orthogonal BODIPY‐Perylene Dyads

Abstract

AbstractBODIPY‐perylene dyads have emerged as useful metal free sensitizers for triplet‐triplet annihilation upconversion (TTAUC), these dyads are capable of efficient triplet generation via spin‐orbit charge transfer intersystem crossing (SOCT‐ISC). This important route to triplet formation requires dyads in which two moieties are oriented perpendicular to each other. In this contribution, we give a deeper insight on the behavior of recently reported BODIPY‐perylene dyads, where BODIPY‐perylene dihedral exhibits a non‐orthogonal dyad geometry. The intersystem crossing of BODIPY‐perylene dyads with and without iodine are investigated using femtosecond transient absorption (fs‐TA) and nanosecond transient absorption (ns‐TA) spectroscopy. The concurrent decay of the singlet charge transfer state (1CT) and rise of triplet states in both the iodinated and non‐iodinated dyads confirms the SOCT‐ISC as the main intersystem crossing pathway despite the altered geometry of the dyads. The presence of an iodine atom on the BODIPY‐moiety enables intersystem crossing 2.6‐times faster and provides a higher triplet yield with respect to dyad without iodine. The upconversion quantum yield ( ) is 8.4‐times higher in the sample containing iodinated dyad as sensitizer and perylene as annihilator. The triplet‐triplet energy transfer rate (kTTET) is ~8×108 M−1 s−1 for both iodinated and non‐iodinated sensitizer containing TTAUC systems in 1,4‐dioxane.