Scientific article
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Maximizing Nanoscale Downshifting Energy Transfer in a Metallosupramolecular Cr(III)–Er(III) Assembly

Published inInorganic chemistry, vol. 63, no. 39, p. 18345-18354
Publication date2024-09-30
First online date2024-08-20
Abstract

Pseudo-octahedral CrIIIN6 chromophores hold a unique appeal for low-energy sensitization of NIR lanthanide luminescence due to their exceptionally long-lived spin-flip excited states. This allure persists despite the obstacles and complexities involved in integrating both elements into a metallosupramolecular assembly. In this work, we have designed a structurally optimized heteroleptic CrIII building block capable of binding rare earths. Following a complex-as-ligand synthetic strategy, two heterometallic supramolecular assemblies, in which three peripherical CrIII sensitizers coordinated through a molecular wire to a central ErIII or YIII, have been prepared. Upon excitation of the CrIII spin-flip states, the downshifted Er(4I13/24I15/2) emission at 1550 nm was induced through intramolecular energy transfer. Time-resolved experiments at room temperature reveal a CrIII-->ErIII energy-transfer of 62-73% efficiencies with rate constants of about 8.5x105 s-1 despite the long donor-acceptor distance (circa 14 Å). This efficient directional intermetallic energy transfer can be rationalized using the Dexter formalism which is promoted by rigid linear electron-rich alkyne bridge that acts as a molecular wire connecting the CrIII and ErIII ions.

Keywords
  • Energy-transfer
  • Chromium
  • Supramolecular
  • Lanthanide
  • Luminescence
Research groups
Citation (ISO format)
PONCET, Maxime Arnaud et al. Maximizing Nanoscale Downshifting Energy Transfer in a Metallosupramolecular Cr(III)–Er(III) Assembly. In: Inorganic chemistry, 2024, vol. 63, n° 39, p. 18345–18354. doi: 10.1021/acs.inorgchem.4c02397
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Article (Accepted version)
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Identifiers
Journal ISSN0020-1669
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