Catalytic and Photoluminescence Properties of the First‐ and Second‐Sphere Coordination of Lanthanide Complexes

Article Article scientifique Article Catalytic and Photoluminescence Properties of the First‐ and Second‐Sphere Coordination of Lanthanide Complexes eng 2025-10-08 2025-11-03 author Le Hoang Giau Department of Inorganic and Analytic Chemistry, University of Geneva, 30 quai E. Ansermet, Geneva, CH-1211, Switzerland. 961440 Chimie minérale groupe 2 (CHAM2) author Guenee Laure Laboratory of Crystallography, University of Geneva, 24 quai E. Ansermet, Geneva, CH-1211, Switzerland. 115015 Département de chimie minérale et analytique (CHIAM) author Delage De Luget Clémence Department of Inorganic and Analytic Chemistry, University of Geneva, 30 quai E. Ansermet, Geneva, CH-1211, Switzerland. 922250 author Chong Julien Department of Inorganic and Analytic Chemistry, University of Geneva, 30 quai E. Ansermet, Geneva, CH-1211, Switzerland. 851973 Chimie minérale groupe 2 (CHAM2) author Piguet Claude 0000-0001-7064-8548 Department of Inorganic and Analytic Chemistry, University of Geneva, 30 quai E. Ansermet, Geneva, CH-1211, Switzerland. 22415 Département de chimie minérale et analytique (CHIAM) e02338 10.1002/chem.202502338 41058516 0947-6539 https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202502338 The efficient binding of receptors Lk (Lk = L5-L8) to [Eu(hfac)3 ] (H-hfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione) allows (i) to gather the basic unit-containing tridentate ligands Lk and the acidic unit-bearing bidentate hfac- co-ligands into a stable single molecular [LkEu(hfac)3 ] adduct working as a catalyst for Michael C─C bond formations, (ii) to enhance the acidity of the N-H units connected to the benzimidazole side arms of the bound ligands L5 and L7, and (iii) to reorganize their geometries into cis-cis conformation for activating Michael substrates 1 and 2 through H-bonding interactions on the second-sphere coordination to provide the target product 3 (up to 92% yield). A maximum enantiomeric excess of 21% could be achieved due to the long distance between the chiral sources and the catalytic sites in the europium complexes. Stepwise distortions from planarity of the terdentate Lk ligands in the yttrium complexes [LkY(hfac)3 ] (Lk = L2, L3, and L5-L10) can be tuned by addition of specific substituent into the benzimidazole side arms, thus realizing some control over their dual fluorescence and phosphorescence emission properties. All [LkEu(hfac)3 ] (Lk = L2, L3, and L5-L10) complexes display europium-centered photoluminescence properties induced by the antenna effect and modulated by the specific design of the light-harvesting aromatic ligand located in the first coordination sphere. Bifunctional catalyst Europium complexes Metal‐template Michael reaction Photoluminescence quantum yield Dewey 540 Swiss National Science Foundation Earth abundant and kinetically inert chromium(III) and iron(II) chromophores for modulating the luminescence of 4f-block cations in (supra)molecular edifices. 207313 CH Projects 40 Département de chimie minérale, analytique et appliquée 145 false 774 Groupe Piguet Chemistry 31 61 fd283a9f-8210-4e95-ad55-4580808f4911 Article (Published version) Public file.pdf 2190346 application/pdf CC BY-4.0 bd1405f7689cf25922c009b795df87fe25e630a5e7d402b9db1be2dc286884e0 openAccess Faculté des sciences / Section de chimie et biochimie / Département de chimie minérale, analytique et appliquée

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Catalytic and Photoluminescence Properties of the First‐ and Second‐Sphere Coordination of Lanthanide Complexes	Chemistry			2025	40	23

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