Preorganized Polyaromatic Soft Terdentate Hosts for the Capture of [Ln(β‐diketonate)3] Guests in Solution

Article Article scientifique Article Preorganized Polyaromatic Soft Terdentate Hosts for the Capture of [Ln(β‐diketonate)3] Guests in Solution eng 2023-01-04 2023-01-04 author Naseri Soroush Department of Inorganic and Analytical Chemistry University of Geneva 30 quai E. Ansermet CH-1211 Geneva 4 Switzerland 906987 Services communs du dépt. de chimie minérale et analytique (CHIMO) author Mirzakhani Mohsen Department of Inorganic and Analytical Chemistry University of Geneva 30 quai E. Ansermet CH-1211 Geneva 4 Switzerland 867142 Département de chimie minérale et analytique (CHIAM) author Besnard Céline Laboratory of Crystallography University of Geneva 24 quai E. Ansermet CH-1211 Geneva 4 Switzerland 682138 Administration de la section de chimie (CHIAD) author Guenee Laure Laboratory of Crystallography University of Geneva 24 quai E. Ansermet CH-1211 Geneva 4 Switzerland 115015 Département de chimie minérale et analytique (CHIAM) author Briant Liza Department of Inorganic and Analytical Chemistry University of Geneva 30 quai E. Ansermet CH-1211 Geneva 4 Switzerland 835743 Département de chimie minérale et analytique (CHIAM) author Nozary Homayoun Department of Inorganic and Analytical Chemistry University of Geneva 30 quai E. Ansermet CH-1211 Geneva 4 Switzerland 86105 Département de chimie minérale et analytique (CHIAM) author Piguet Claude 0000-0001-7064-8548 Department of Inorganic and Analytical Chemistry University of Geneva 30 quai E. Ansermet CH-1211 Geneva 4 Switzerland 22415 Département de chimie minérale et analytique (CHIAM) 10.1002/chem.202202727 36285628 0947-6539 https://onlinelibrary.wiley.com/doi/10.1002/chem.202202727 The concept of preorganization is famous in coordination chemistry for having transformed flexible bidentate 2,2’-bipyridine scaffolds into rigid 1,10-phenanthroline platforms. The resulting boosted affinities for d-block cations has successfully paved the way for the design of a wealth of functional complexes, devices and materials for analysis and optics. Its extension toward terdentate homologues adapted for the selective complexation of f-block cations with larger coordination numbers remains more overlooked. The resulting rigidification of 2,6-bis(1-methyl-1H-benzo[d]imidazol-2-yl)pyridine ligands (L1–L7) produces the highly preorganized and extended polyaromatic benzo[4′,5′]imidazo[1′,2′ : 1,2]pyrido[3,4-b]benzo[4,5]imidazo[1,2-h][1,7]naphthyridines (L8–L11) receptors, which offer some novel and rare opportunities for efficiently complexing trivalent lanthanides with polyaromatic soft terimine ligands. The crystal structures of the stable heteroleptic [LkLn(hfac)3] adducts (Lk=L1, L8, L9; Ln=La, Eu, Gd, Er, Yb, Y; H-hfac=1,1,1,5,5,5-hexafluoropentane-2,4-dione) show a drastic decrease in the Ln−N bond valences upon replacement of the flexible ligand L1 with its preorganized counterparts L8 and L9. This points to a limited match between the preorganized cavity and the entering [Ln(hfac)3] lanthanide containers. However, thermodynamic studies conducted in dichloromethane reach the opposite conclusion, with an improved affinity, by up to three orders of magnitude for catching Ln(hfac)3 when L1 is replaced by the preorganized L8–L9 receptors. The key to the enigma lies in the removal of the energy penalty which accompanies the formation of flexible [L1Ln(hfac)3] complexes in solution. This driving force overcomes the poor match between the preorganized terdentate N∩N∩N cavity in L8 and L9 and the size of trivalent lanthanides. As planned, the rigid, planar and extended π-conjugated system found in L8 and L9 shifts the ligand-centered absorption bands by about 5000 cm−1 toward lower energies, a crucial point if these stable [L8Ln(hfac)3] and [L9Ln(hfac)3] platforms have to be considered for the visible sensitization of luminescent lanthanides in metallopolymers. Host-guest Lanthanide Preorganization Thermodynamics Tridentate receptor Dewey 540 Swiss National Science Foundation Can Functional Metallopolymers and Supramolecular Assemblies Benefit from Molecular Organization Mastered by Coordination Chemists ? 178758 CH Projects 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 29 10 188388a7-d181-49cd-a3f1-a3bb0e84043e Article (Accepted version) Public Preorganized_tridentate_text_deposi.pdf 965913 application/pdf Restricted 2024-01-05 6c392d6b58e637b5f0746f5e6d0742f12a3e12e3d225a00df84fa9742a57be75 1b06bb74-b296-46a0-a34a-ecf2fd2176ab Article (Published version) Restricted Naseri_CaEJ_2022.pdf 14625245 application/pdf f0a3ed1a5104b690cb2bd67bb5714d8fd5989d29d10145b43b01685fa789340a Vignette Public chem202202727-toc-0001-m.webp 91634 image/png openAccess Faculté des sciences / Section de chimie et biochimie / Département de chimie minérale, analytique et appliquée

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