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.

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