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The resulting boosted affinities for d\u2010block 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\u2010block cations with larger coordination numbers remains more overlooked. The resulting rigidification of 2,6\u2010bis(1\u2010methyl\u20101<jats:italic>H<\/jats:italic>\u2010benzo[d]imidazol\u20102\u2010yl)pyridine ligands (<jats:bold>L1<\/jats:bold>\u2013<jats:bold>L7<\/jats:bold>) produces the highly preorganized and extended polyaromatic benzo[4\u2032,5\u2032]imidazo[1\u2032,2\u2032\u2009:\u20091,2]pyrido[3,4\u2010b]benzo[4,5]imidazo[1,2\u2010h][1,7]naphthyridines (<jats:bold>L8<\/jats:bold>\u2013<jats:bold>L11<\/jats:bold>) 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 [<jats:bold>L<jats:italic>k<\/jats:italic><\/jats:bold>Ln(hfac)<jats:sub>3<\/jats:sub>] adducts (<jats:bold>L<jats:italic>k<\/jats:italic><\/jats:bold>=<jats:bold>L1<\/jats:bold>, <jats:bold>L8<\/jats:bold>, <jats:bold>L9<\/jats:bold>; Ln=La, Eu, Gd, Er, Yb, Y; H\u2010hfac=1,1,1,5,5,5\u2010hexafluoropentane\u20102,4\u2010dione) show a drastic decrease in the Ln\u2212N bond valences upon replacement of the flexible ligand <jats:bold>L1<\/jats:bold> with its preorganized counterparts <jats:bold>L8<\/jats:bold> and <jats:bold>L9<\/jats:bold>. This points to a limited match between the preorganized cavity and the entering [Ln(hfac)<jats:sub>3<\/jats:sub>] 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)<jats:sub>3<\/jats:sub> when <jats:bold>L1<\/jats:bold> is replaced by the preorganized <jats:bold>L8<\/jats:bold>\u2013<jats:bold>L9<\/jats:bold> receptors. The key to the enigma lies in the removal of the energy penalty which accompanies the formation of flexible [<jats:bold>L1<\/jats:bold>Ln(hfac)<jats:sub>3<\/jats:sub>] complexes in solution. This driving force overcomes the poor match between the preorganized terdentate N<jats:sup>\u2229<\/jats:sup>N<jats:sup>\u2229<\/jats:sup>N cavity in <jats:bold>L8<\/jats:bold> and <jats:bold>L9<\/jats:bold> and the size of trivalent lanthanides. As planned, the rigid, planar and extended \u03c0\u2010conjugated system found in <jats:bold>L8<\/jats:bold> and <jats:bold>L9<\/jats:bold> shifts the ligand\u2010centered absorption bands by about 5000\u2005cm<jats:sup>\u22121<\/jats:sup> toward lower energies, a crucial point if these stable [<jats:bold>L8<\/jats:bold>Ln(hfac)<jats:sub>3<\/jats:sub>] and [<jats:bold>L9<\/jats:bold>Ln(hfac)<jats:sub>3<\/jats:sub>] platforms have to be considered for the visible sensitization of luminescent lanthanides in metallopolymers.<\/jats:p>","DOI":"10.1002\/chem.202202727","type":"journal-article","created":{"date-parts":[[2022,10,26]],"date-time":"2022-10-26T04:55:35Z","timestamp":1666760135000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":16,"title":["Preorganized Polyaromatic Soft Terdentate Hosts for the Capture of [Ln(<i>\u03b2<\/i>\u2010diketonate)<sub>3<\/sub>] Guests in Solution"],"prefix":"10.1002","volume":"29","author":[{"given":"Soroush","family":"Naseri","sequence":"first","affiliation":[{"name":"Department of Inorganic and Analytical Chemistry University of Geneva  30 quai E. 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