Metal-Assisted Synthesis of Extended Polyaromatic Nitrogen-Rich Ligands for Tunable Sensitization of Eu(III) Complexes

Article Article scientifique Article Metal-Assisted Synthesis of Extended Polyaromatic Nitrogen-Rich Ligands for Tunable Sensitization of Eu(III) Complexes eng 2025-02-17 author Le Hoang Giau Department of Inorganic and Analytical Chemistry, University of Geneva, 30 quai E. Ansermet, CH-1211 Geneva, Switzerland. 961440 Chimie minérale groupe 2 (CHAM2) author Guenee Laure Laboratory of Crystallography, University of Geneva, 24 quai E. Ansermet, CH-1211 Geneva, Switzerland. 115015 Département de chimie minérale et analytique (CHIAM) author Bertrand-Avebe Melanda Department of Inorganic and Analytical Chemistry, University of Geneva, 30 quai E. Ansermet, CH-1211 Geneva, Switzerland. 402710 Unité de formation des apprentis (UFA) author Babel Lucille Department of Inorganic and Analytical Chemistry, University of Geneva, 30 quai E. Ansermet, CH-1211 Geneva, Switzerland. 652456 Département de chimie minérale et analytique (CHIAM) Lucille Simond author Rosspeintner Arnulf 0000-0002-1828-5206 Department of Physical Chemistry, University of Geneva, 30 quai E. Ansermet, 1211 Geneva, Switzerland. 723857 Département de chimie physique (CHIFI) author Piguet Claude 0000-0001-7064-8548 Department of Inorganic and Analytical Chemistry, University of Geneva, 30 quai E. Ansermet, CH-1211 Geneva, Switzerland. 22415 Département de chimie minérale et analytique (CHIAM) 3941-3958 4c05202 10.1021/acs.inorgchem.4c05202 39960749 0020-1669 https://pubs.acs.org/doi/10.1021/acs.inorgchem.4c05202 We report the metal-assisted synthesis of oligomeric nitrogen-rich DiL1 and PoL1 n sensitizers from the monomer L1 via acyclic diene metathesis (ADMET) polymerization for the tuning of the photoluminescence properties of europium-containing complexes by ligand design. The binding of [Eu(hfac)3 ] cargoes (H-hfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione) to monomer L1 to give [L1 Eu(hfac)3 ] during metathesis appeared to be essential (i) for protecting the Grubbs ruthenium catalyst to interact with the nitrogen atoms of L1 and (ii) to drive the Ru-catalyzed ADMET reaction toward dimeric {DiL1 [Eu(hfac)3 ]2 } and polymeric {PoL1 n [Eu(hfac)3 ] n } assemblies. Compared with the monomeric tridentate L1 -L4 ligands, significant electronic delocalization occurs through the π-conjugated benzimidazole-CH═CH-benzimidazole skeletons in the dimer DiL1 and polymers PoL1 n , which results in a stepwise red-shift of the excited levels in these extended polyaromatic ligands. As a consequence, the sensitization of bound [Eu(hfac)3 ] units reveals a decrease of the photoluminescence quantum yields along the [L4 Eu(hfac)3 ] > [L3 Eu(hfac)3 ] > [L2 Eu(hfac)3 ] ≈ [L1 Eu(hfac)3 ] > {DiL1 [Eu(hfac)3 ]2 } > {PoL1 18 [Eu(hfac)3 ]18 } series due to unfavorable europium-to-ligand back energy transfers. 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 38 Département de chimie physique 142 40 Département de chimie minérale, analytique et appliquée 145 false 694 Groupe Bürgi 774 Groupe Piguet Inorganic chemistry 64 8 26a05a9a-1cd2-4888-b087-e30e1792e5ed Article (Published version) Restricted le-hoang-et-al-2025-metal-assisted-.pdf 5825575 application/pdf b0959ff8ac0a01024bc5162aa680e0a97968873120a1cc60bbe2c4155a7af5ad 4614a7da-d961-4ee6-93d2-ec509f523a8c Article (Accepted version) Public Polymer-LHGiau_text_deposited(1).pdf 1419887 application/pdf Restricted 2026-02-18 bd8100df18e78c477ec26ea955b92f95a13aa961c10b3496c26d241e2be9ca75 embargoedAccess Faculté des sciences / Section de chimie et biochimie / Département de chimie physique Faculté des sciences / Section de chimie et biochimie / Département de chimie minérale, analytique et appliquée

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Metal-Assisted Synthesis of Extended Polyaromatic Nitrogen-Rich Ligands for Tunable Sensitization of Eu(III) Complexes	Inorganic chemistry	2025	141	0
A Rational Approach to Metal Loading of Organic Multi-Site Polymers: Illusion or Reality?	Chemistry - A European Journal	2018	670	471

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