New NIR-luminescent lanthanide complexes with tridentate oxybenzophenanthroline ligands

Balashova, T. V.; Arsenyev, Maxim V.; Polyakova, Svetlana; Ilichev, V. A.; Rumyantcev, Roman V.; Fukin, Georgy K.; Yablonskiy, A. N.; Bochkarev, M. N.

doi:10.1039/d3nj00625e

Cited by 2 publications

(1 citation statement)

References 56 publications

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“…For the current work, we initiated studies of cerium complexes of redox-active amido-phenolate-type ligands, comprising the tris(2-(3′,5′-di- tert -butyl-2′-hydroxyphenyl)amino-phenyl) amine (H 6 Clamp) and 4,6-di- tert -butyl-2-[(2,6-diisopropylphenyl)imino]quinone (ap) proligands. In addition to catecholates and pyridine(diimines), − amido-phenolates comprise some of the most-studied platforms in the chemistry of metal–ligand redox cooperativity. − For the two ligand systems studied here, the primary structural differences between them are that the tethered, tripodal H 3 Clamp 3– ligands include amine protons and are geometrically restricted to create rigid metal-ion cryptates, whereas the amido-phenolate (ap 2– ) ligands comprise a heterobimetallic complex K 3 (THF) 3 Ce III ( dipp ap) 3 where the potassium cations show bridging interactions between ap 2– ligand oxygen atoms in the solid state. As such, the heterobimetallic framework is expected to allow for free ligand reorganization upon cerium oxidation.…”

Section: Introductionmentioning

confidence: 99%

Metal–Ligand Redox Cooperativity in Cerium Amine-/Amido-Phenolate-Type Complexes

Uruburo,

Y. P. Rupasinghe,

Gupta

et al. 2023

Inorg. Chem.

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The synthesis and characterization of two cerium complexes of redox-active amine/amido-phenolate-type ligands are reported. A tripodal framework comprising the tris(2-(3′,5′-di-tertbutyl-2′-hydroxyphenyl)amino-phenyl) amine (H 6 Clamp) proligand was synthesized for comparison of its cerium complex with a potassium−cerium heterobimetallic complex of the 4,6-di-tert-butyl-2- [(2,6-diisopropylphenyl)imino]quinone ( dipp ap) proligand. Structural studies indicate differences in the cerium(III) cation coordination spheres, where Ce III (CH 3 CN) 1.5 (H 3 Clamp) (1-Ce(H 3 Clamp)) exhibits shorter Ce−O distances and longer Ce−N bond distances compared to the analogous distances in K 3 (THF) 3 Ce III ( dipp ap) 3 (2-Ce(ap)), due to the gross structural differences between the systems. Differences are also evident in the temperature-dependent magnetic properties, where smaller χT products were observed for 2-Ce(ap) compared to 1-Ce(H 3 Clamp). Solution electrochemical studies for the complexes were interpreted based on ligand-and metal-based oxidation events, and the cerium(III) oxidation of 2-Ce(ap) was observed to be more facile than that of 1-Ce(H 3 Clamp), behavior that was cautiously attributed to the rigidity of the encrypted 1-Ce(H 3 Clamp) complex compared to the heterobimetallic framework of 2-Ce(ap). These results contribute to the understanding of how ligand designs can promote facile redox cycling for cerium complexes of redox-active ligands, given the large contraction of cerium−ligand bonds upon oxidation.

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Section: Introductionmentioning

confidence: 99%

Metal–Ligand Redox Cooperativity in Cerium Amine-/Amido-Phenolate-Type Complexes

Uruburo,

Y. P. Rupasinghe,

Gupta

et al. 2023

Inorg. Chem.

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Enantioselective Michael addition of malonates to α,β-unsaturated ketones catalyzed by rare-earth metal amides RE[N(SiMe3)2]3 with phenoxy-functionalized amino alcohol proligands

Yang,

et al. 2024

Tetrahedron Letters

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New NIR-luminescent lanthanide complexes with tridentate oxybenzophenanthroline ligands

Abstract: Complexes of La (1), Sm (2), Gd (3), Er (4) and Yb (5) with benzophenanthroline derivative ligands were synthesized under mild conditions by reactions of 8,10-di-tert-butylbenzo[b][1,10]phenanthrolin-11-ol (H(bphen)) with tris(trimethylsilyl)amides of...

Cited by 2 publications

References 56 publications

Metal–Ligand Redox Cooperativity in Cerium Amine-/Amido-Phenolate-Type Complexes

Metal–Ligand Redox Cooperativity in Cerium Amine-/Amido-Phenolate-Type Complexes

Enantioselective Michael addition of malonates to α,β-unsaturated ketones catalyzed by rare-earth metal amides RE[N(SiMe3)2]3 with phenoxy-functionalized amino alcohol proligands

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