Near Infrared–Circularly Polarized Luminescence/Circular Dichroism Active Yb(III) Complexes Bearing Both Central and Axial Chirality

In this contribution, we present new NIR-CPL/CD active Yb(III) complexes, which are synthesized by combining two ligands characterized by different types of chirality: central and axial chirality. The ligand bearing central chirality is represented by the neutral <i>trans</i>-<i>N</i>,<i>N</i>'-bis(2-pyridylmethylidene)-1,2-(<i>R</i>,<i>R</i> or <i>S</i>,<i>S</i>) cyclohexanediamine (<b>L</b>), whereas the axial ligand is 1,1'-binaphthyl-2,2'-diol (BINOL-H<sub>2</sub>). A combined <sup>1</sup>H NMR, thermodynamic (spectrophotometric titrations), and theoretical (DFT structural calculations) study is presented, revealing the high stability in the methanol solution of the homochiral <i>C</i><sub><i>2</i></sub>-symmetric anionic [Yb<b>L</b>(BINOL)<sub>2</sub>]<sup>-</sup> complexes, in which the two labile BINOLate molecules exhibit the same stereochemistry (<i>R</i> or <i>S</i>). The metal ion-related optical and chiroptical properties of the complexes in the near-infrared spectral region are here presented and discussed: while the axial chirality dominates the circularly polarized luminescence features, the NIR-CD signal is affected by both chiral elements.

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Publication Details

Journal
Inorganic Chemistry
Published
2025-03-13
DOI
https://doi.org/10.1021/acs.inorgchem.4c05420
Citations
7
Primary Topic
Lanthanide and Transition Metal Complexes
Type
article
Field-Weighted Citation Impact
3.62

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article

Near Infrared–Circularly Polarized Luminescence/Circular Dichroism Active Yb(III) Complexes Bearing Both Central and Axial Chirality

Andrea Melchior, Silvia Ruggieri, Mariafrancesca Fochi, Fabio Piccinelli et al.
7 citations
Inorganic Chemistry
Lanthanide and Transition Metal Complexes
3.62
article

Near Infrared–Circularly Polarized Luminescence/Circular Dichroism Active Yb(III) Complexes Bearing Both Central and Axial Chirality

Andrea Melchior, Silvia Ruggieri, Mariafrancesca Fochi, Fabio Piccinelli, Francesco Zinna, Enrico Cavalli, Oliver G. Willis, Luca Bernardi, Lorenzo Di Bari, Giorgiana Denisa Bisag, Martina Sanadar, Silvia Mizzoni
article en
7 citations

Abstract

In this contribution, we present new NIR-CPL/CD active Yb(III) complexes, which are synthesized by combining two ligands characterized by different types of chirality: central and axial chirality. The ligand bearing central chirality is represented by the neutral <i>trans</i>-<i>N</i>,<i>N</i>'-bis(2-pyridylmethylidene)-1,2-(<i>R</i>,<i>R</i> or <i>S</i>,<i>S</i>) cyclohexanediamine (<b>L</b>), whereas the axial ligand is 1,1'-binaphthyl-2,2'-diol (BINOL-H<sub>2</sub>). A combined <sup>1</sup>H NMR, thermodynamic (spectrophotometric titrations), and theoretical (DFT structural calculations) study is presented, revealing the high stability in the methanol solution of the homochiral <i>C</i><sub><i>2</i></sub>-symmetric anionic [Yb<b>L</b>(BINOL)<sub>2</sub>]<sup>-</sup> complexes, in which the two labile BINOLate molecules exhibit the same stereochemistry (<i>R</i> or <i>S</i>). The metal ion-related optical and chiroptical properties of the complexes in the near-infrared spectral region are here presented and discussed: while the axial chirality dominates the circularly polarized luminescence features, the NIR-CD signal is affected by both chiral elements.

Inorganic ChemistryVol. 64(11)
University of Pisa (IT), University of Verona (IT), University of Parma (IT), University of Udine (IT), University of Bologna (IT)
Ministero dell’Istruzione, dell’Università e della Ricerca
Openalex Percentile: Top 7%
Lanthanide and Transition Metal Complexes
3.62
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