High Quantum Yields from Perfluorinated Binolate Erbium Complexes and Their Circularly Polarized Luminescence

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(10), P. 7097 - 7104

Published: Feb. 27, 2024

High quantum yield and circularly polarized luminescence (CPL) brightness values are reported from Shibasaki-type erbium complexes supported by a perfluorinated Binol ligand (F12Binol). The total fluorination of the circumvents nonradiative quenching Csp2-H vibrations leads to yields up 11% CPL 317 M–1 cm–1 (a 19- 6-fold increase, respectively, compared (Binol)3ErNa3). These highest for any molecular complex date, making them comparable Yb emitters. A series fluorinated synthesized varying alkali metal (K, Na, Li) in secondary coordination sphere, leading unexpected structural differences. NMR (19F, 7Li) chiroptical spectroscopy analyses provide insights into their geometry. With much improved values, we synthetic design principles toward other practical candidates use communication technologies.

Language: Английский

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Solvent induced self-assembly of dinuclear Eu(III) helicate and emergent strong CPL

Dalton Transactions, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

The assembly shows the structural transformation from a multiple species mixture Eu 2 (LR) n to helicate 4 upon increasing content of CHCl 3 in CH CN, which was accompanied by an enhanced CPL activity.

Language: Английский

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Two pairs of chiral Yb^III enantiomers presenting distinct NIR luminescence and circularly polarized luminescence performances with giant differences in second-harmonic generation responses

Dalton Transactions, Journal Year: 2023, Volume and Issue: 52(47), P. 17758 - 17766

Published: Jan. 1, 2023

By introducing enantiomerically pure mono-bidentate N-donor ligands (LR/LS) into Yb(btfa)3(H2O)2 and Yb(dbm)3(H2O), respectively, two pairs of chiral YbIII enantiomers, namely Yb(btfa)3LR/Yb(btfa)3LS (D-1/L-1) [Yb(dbm)3LR]·[Yb(dbm)3(C2H5OH)]/[Yb(dbm)3LS]·[Yb(dbm)3(C2H5OH)] (D-2/L-2) were isolated, where btfa- = 3-benzoyl-1,1,1-trifluoroacetonate, dbm- dibenzoylmethanate, LR/LS (-)/(+)-4,5-pinenepyridyl-2-pyrazine. D-1/L-1 possess mononuclear structures in which the ions are eight-coordinated, while D-2/L-2 show cocrystal containing Yb(dbm)3(LR/LS) Yb(dbm)3(C2H5OH) moieties eight seven-coordinated, respectively. They not only feature different molecular but also present distinct linear nonlinear optical performances. Chiral D-1 has better near infrared photo-luminescence (NIR-PL) circularly polarized luminescence (CPL) performances than D-2. More remarkably, large second-harmonic generation (SHG) responses (up to 1.25/1.28 × KDP) 18/16 times those (0.07/0.08 KDP). In addition, represent first examples lanthanide complexes with NIR-PL, NIR-CPL SHG properties.

Language: Английский

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Circularly polarized luminescence activity in the near infrared spectral region of a water-soluble ytterbium(iii) complex containing a conjugated chromophoric ligand

New Journal of Chemistry, Journal Year: 2024, Volume and Issue: 48(21), P. 9627 - 9636

Published: Jan. 1, 2024

A chiral Yb( iii ) complex bearing a conjugated chromophoric ligand exhibits potential as NIR-to-NIR chiroptical probe for biological purposes.

Language: Английский

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Augmentation of NIR Circularly Polarized Luminescence Activity in Shibasaki-Type Lanthanide Complexes Supported by the Spirane Sphenol

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(16), P. 7378 - 7385

Published: April 5, 2024

We report two new circularly polarized luminescence (CPL)-active lanthanide complexes emissive in the near-infrared (NIR) region; using sphenol as a supporting ligand, we provide first reported example of an NIR-emissive complex supported by chiral spirane. Inclusion quaternary carbon to impart axial chirality results dramatic augmentation CPL strength resultant sphenolate (glum ≤ 0.77 for [(sphenol)3ErNa3(thf)6]) compared that their contemporary biaryl-based axially analogues 0.47 [(binol)3ErNa3(thf)6]). Despite similar structural parameters, rigid spiro enables strongest dissymmetry factors observed date from Shibasaki-type both Yb and Er. also demonstrate sensitivity chiroptical measurements small variations instrumental such bandpass, suggest standardized method or at least additional detail should be included future reports allow direct comparisons between newly published emitters.

Language: Английский

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Lanthanide luminescent di-metallic triple-stranded helicates formed from bis-tridentate (1,2,3-triazol-4-yl)-picolinamide (tzpa) ligands and their higher order self-assemblies

Materials Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 9(2), P. 258 - 270

Published: Nov. 14, 2024

The bis-tridentate (1,2,3-triazol-4-yl)-picolinamide (tzpa) ligands 1 and 2 were used in the formation of luminescent di-metallic Tb( iii ) triple stranded helicates 3 4 (L Tb ; L = or 2).

Language: Английский

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Significantly boosting circularly polarized luminescence by synergy of helical and planar chirality

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: unknown, P. 110724 - 110724

Published: Dec. 1, 2024

Language: Английский

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Controllable chiral memory in an anion tetrahedral cage

Inorganic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(21), P. 6384 - 6391

Published: Jan. 1, 2023

The chiral induction of a series biomolecules to an anion-coordination-driven tetrahedral cage 1 was presented in this work, followed by memory effect upon replacing the guests with achiral ones.

Language: Английский

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