Host−guest complexation-mediated supramolecular photon upconversion

Abstract

The phenomenon of photon upconversion, in which a system absorbs two or more photons of lower energy and emits a photon of higher energy, has been used in numerous applications, including non-destructive bioimaging, deep-penetrating photodynamic therapy, catalysis, and photovoltaic devices. To date, photon upconversion has been observed typically in inorganic nanocrystals, nanoparticles, metal−organic frameworks, supramolecular assemblies, and organic dyads. Herein, we demonstrate a new strategy for harnessing photon upconversion-supramolecular upconversion-based on host−guest chemistry. We have identified a box-like fluorescent tetracationic host incorporating a thiazolothiazole emitter, which can accommodate a guest-sensitizer, 5,15-diphenylporphyrin, inside its cavity, and demonstrated that the host−guest inclusion complex displays triplet-fusion upconversion when the guest is excited with low-energy light. The strategy of supramolecular upconversion has been employed successfully in two other host−guest complexes-with hosts comprised of anthracene emitters and a 5,15-diphenylporphyrin guest-corroborating the fact that this strategy is a general one and can be applied to the design of a new family of host−guest complexes for photon upconversion. More importantly, supramolecular upconversion is accessible in solution under dilute conditions (μM) compared to most of the existing approaches that require significantly higher concentrations (mM) of emitters and/or sensitizers. Transient absorption spectroscopy and density functional theory have been employed in order to confirm a triplet-fusion upconversion mechanism. Host−guest complexation-mediated supramolecular photon upconversion eliminates multiple issues in the existing systems related to high working concentrations, high incident laser power, and low optical penetration depths.