A hybrid molecular sensitizer for triplet fusion upconversion

Abstract

Triplet fusion upconversion is useful for a broad spectrum of applications ranging from solar cells, photoredox catalysis, to biophotonics applications, especially in the near-infrared (NIR, >700 nm) range. This upconverting system typically demands efficient conversion of spin-singlet harvested energy through intersystem crossing to spin-triplet states, accessible only in rare metallic-coordinating macrocycle compounds or heavy-metal-containing semiconductor quantum dots for triplet sensitization. Herein, we describe an organic–inorganic system for NIR-to-visible triplet fusion upconversion, interfacing commonly-seen, non-metallic, infrared dyes (IR806, IR780, indyocynine green, and CarCl) and lanthanide nanocrystal (sodium ytterbium fluoride) as a hybrid molecular sensitizer, which extracts molecular spin-singlet energy to nanocrystal-enriched ytterbium dopants at ~48% efficiency (IR806, photoexciation at 808 nm). Moreover, ytterbium sub-lattice energy migration increases the interaction possibility between the nanocrystal and the freely-diffusing rubrenes in solution, resulting in 24-fold (IR806) to 1740-fold (indocyanine green) upconversion (600 nm) increase, depending on the IR dye type, as compared to the one without ytterbium nanotransducers. Ab initio quantum chemistry calculations identify enhanced spin-orbital coupling in the ytterbium-IR806 complex and high energy transfer rate in the ytterbium-rubrene interaction (1010 s−1). Employing inorganic lanthanide nanocrystals as nanotransducers unleashes the potential use of non-metallic infrared organic dyes for triplet fusion upconversion.