Please use this identifier to cite or link to this item:
|Raw data for "Coulomb interactions for mediator-enhanced sensitized triplet-triplet annihilation upconversion in solution"
|Online publication date:
|Year of first publication:
|Sensitized triplet-triplet annihilation upconversion offers an attractive possibility to replace a high-energy photon by two photons with lower energy through the combination of a light-harvesting triplet sensitizer and an annihilator for the formation of a fluorescent singlet state. Typically, high annihilator concentrations are required to achieve an efficient initial energy transfer and as a direct consequence the most highly energetic emission is often not detectable due to intrinsic reabsorption by the annihilator itself. Herein, we demonstrate that the addition of a charge-adapted mediator drastically improves the energy transfer efficiency at low annihilator concentrations via an energy transfer cascade. Inspired by molecular dyads and recent developments in nanocrystal-sensitized upconversion, our system exploits a concept to minimize intrinsic filter effects, while boosting the upconversion quantum yield in solution. A sensitizer-annihilator combination consisting of a ruthenium-based complex and 9,10-diphenylanthracene (DPA) is explored as model system and a sulfonated pyrene serves as mediator. The impact of opposite charges between sensitizer and mediator – to induce Coulombic attraction and subsequently result in accelerated energy transfer rate constants – is analyzed in detail by different spectroscopic methods. Ion pairing and the resulting static energy transfer in both directions is a minor process, resulting in an improved overall performance. Finally, the more intense upconverted emission in the presence of the mediator is used to drive two catalytic photoreactions in a two-chamber setup, illustrating the advantages of our approach, in particular for photoreactions requiring oxygen that would interfere with the upconversion system.
540 Chemistry and allied sciences
|Johannes Gutenberg-Universität Mainz
|FB 09 Chemie, Pharmazie u. Geowissensch.
|Information on rights of use:
|is source of 10.1039/D3NR05265F
|Appears in collections:
Files in This Item:
|Raw data for figures in the main manuscript