A hydrogen-bond-stabilized chiral tetrakis Eu( <scp>iii</scp> ) complex with strong circularly polarized luminescence

We report the synthesis and properties of a hydrogen-bond-stabilized chiral tetrakis Eu(III) complex with enhanced circularly polarized luminescence (CPL). It is based on a Eu(III) tris[3-(heptafluoropropylhydroxymethylene)-camphorate] complex modified with tetrabutylammonium and imidazolium counterions. While the bulky tetrabutylammonium cation preserves the parent tris-diketonate framework, the smaller imidazolium cation forms a novel chiral tetrakis Eu(III) complex through stable NH⋯OC hydrogen bonding between the imidazolium N-H donor and the diketonate carbonyl acceptor. A single-crystal X-ray diffraction study indicates a square-antiprismatic geometry. CPL spectra, recorded with a Raman optical activity (ROA) spectrometer under 532 nm excitation, reveal an extremely high dissymmetric factor of 1.26 at 595 nm. In chloroform solution, additional ROA signals were detected, attributed to CPL-induced Raman scattering from the solvent. These properties highlight the convenience of hydrogen-bond-assisted stabilization. The results document an efficient approach for tuning CPL-active lanthanide complexes and demonstrate the methodological advantage of ROA-based CPL detection.

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Publication Details

Journal
Dalton Transactions
Published
2025-01-01
DOI
https://doi.org/10.1039/d5dt02294k
Primary Topic
Lanthanide and Transition Metal Complexes
Type
article
Field-Weighted Citation Impact
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article

A hydrogen-bond-stabilized chiral tetrakis Eu( iii ) complex with strong circularly polarized luminescence

Tao Wu, Kun Qian, Petr Bouř, Blanka Klepetářová
Dalton Transactions
Lanthanide and Transition Metal Complexes
article

A hydrogen-bond-stabilized chiral tetrakis Eu( iii ) complex with strong circularly polarized luminescence

Tao Wu, Kun Qian, Petr Bouř, Blanka Klepetářová
article en

Abstract

We report the synthesis and properties of a hydrogen-bond-stabilized chiral tetrakis Eu(III) complex with enhanced circularly polarized luminescence (CPL). It is based on a Eu(III) tris[3-(heptafluoropropylhydroxymethylene)-camphorate] complex modified with tetrabutylammonium and imidazolium counterions. While the bulky tetrabutylammonium cation preserves the parent tris-diketonate framework, the smaller imidazolium cation forms a novel chiral tetrakis Eu(III) complex through stable NH⋯OC hydrogen bonding between the imidazolium N-H donor and the diketonate carbonyl acceptor. A single-crystal X-ray diffraction study indicates a square-antiprismatic geometry. CPL spectra, recorded with a Raman optical activity (ROA) spectrometer under 532 nm excitation, reveal an extremely high dissymmetric factor of 1.26 at 595 nm. In chloroform solution, additional ROA signals were detected, attributed to CPL-induced Raman scattering from the solvent. These properties highlight the convenience of hydrogen-bond-assisted stabilization. The results document an efficient approach for tuning CPL-active lanthanide complexes and demonstrate the methodological advantage of ROA-based CPL detection.

Dalton TransactionsVol. 54(48)
Jiangxi University of Traditional Chinese Medicine (CN), Czech Academy of Sciences, Institute of Organic Chemistry and Biochemistry (CZ)
National Natural Science Foundation of China, Grantová Agentura České Republiky
Openalex Percentile: Top 74%
Lanthanide and Transition Metal Complexes
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A hydrogen-bond-stabilized chiral tetrakis Eu( <scp>iii</scp> ) complex with strong circularly polarized luminescence — Tao Wu, Kun Qian, et al. · Dalton Transactions (2025) | TGRS Research Map | TGRS