Excited states engineering maximizes singlet generation by triplet fusion in conjugated systems

TL;DR

This paper presents a molecular design strategy to enhance singlet generation in triplet-triplet annihilation upconversion, achieving high yields and low excitation thresholds suitable for solar energy applications.

Contribution

The authors engineered a naphthalene-derived annihilator with an excited state landscape that maximizes singlet formation, improving upconversion efficiency under low light conditions.

Findings

Achieved up to 0.83 singlet yield in engineered molecules.

Delivered UV/visible upconversion peaking at 390 nm.

Lowered activation excitation intensity threshold below 0.1 suns.

Abstract

Photon upconverters are anti Stokes emitters capable of generating photons with higher energy than those absorbed. This behavior can be achieved through different mechanisms, which are extensively studied for applications in imaging, anticounterfeiting, information encryption and most importantly, solar energy technologies. Among these mechanisms, photon upconversion based on sensitized triplet-triplet annihilation (sTTA-UC) is particularly attractive because it operates under low intensity, incoherent light. In sTTA UC, two optically dark triplet states of a conjugated annihilator fuse upon collision to populate a higher energy fluorescent singlet, with the triplets initially generated via energy transfer from a lower energy sensitizer. Here we introduce a general molecular design strategy to maximize singlet generation through TTA. By selective substitution, we engineered a naphthalene derived annihilator with an excited state energy landscape that strongly favors singlet formation, achieving yields up to 0.83. When combined with an appropriate triplet sensitizer, the system delivers stable UV/visible upconversion peaking at 390 nm, with an absolute upconversion yield about 0.19 and an activation excitation intensity threshold lower than 0.1 suns under non-coherent broadband excitation fully compatible with the requirements of solar powered technologies.