Journal Articles Physical Chemistry Chemical Physics Year : 2024

Temperature-dependent NIR-CPL spectra of chiral Yb(iii) complexes

Annika Sickinger
Laure Guy
Yannick Guyot
Olivier Cador
Stephan Guy
Olivier Maury

Abstract

Chiral, enantiopure Yb(III) complexes exhibit circularly polarized luminescence (CPL) in the near infrared (NIR) wavelength region. This CPL is quantified by the dissymmetry factor (). The excited state F consists of six m states degenerated in three Stark levels, due to the crystal-field splitting (CFS), which are populated in accordance with the Boltzmann distribution. Consequently, room temperature CPL spectra are the sum of various - either positive or negative - contributions, that are practically impossible to quantify. To address this issue, an advanced setup enabling CPL measurements over a broad temperature range (300 to 4 K) has been developed. The interrelation of CFS, and temperature was explored using a pair of enantiopure Yb(III) complexes, highlighting the individual contribution of each crystal-field sublevel to the overall CPL spectrum, as anticipated by simulations performed in the framework of multireference wave-functions. Hence, the CPL spectra of chiral lanthanide complexes were found to be indeed strongly temperature-dependent, as is the dissymmetry factor, as a consequence of the variation in thermal sublevel population.
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hal-04594117 , version 1 (30-05-2024)

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Annika Sickinger, Maxime Grasser, Bruno Baguenard, Amina Bensalah-Ledoux, Laure Guy, et al.. Temperature-dependent NIR-CPL spectra of chiral Yb(iii) complexes. Physical Chemistry Chemical Physics, 2024, 26 (21), pp.15776-15783. ⟨10.1039/D4CP01286K⟩. ⟨hal-04594117⟩
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