American Chemical Society
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Bent 1,10-Phenanthroline Ligands within Octahedral Complexes Constructed around a TiO4N2 Core

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journal contribution
posted on 2020-08-12, 23:03 authored by Matthieu Scarpi-Luttenauer, Loris Geminiani, Pauline Lebrun, Nathalie Kyritsakas, Alain Chaumont, Marc Henry, Pierre Mobian
The synthesis of monomeric octahedral complexes constructed around a TiO4N2 core bearing neocuproine derivatives is detailed. These architectures follow the [Ti­(1)2(N-N)] general formulas, where 1 is the 6,6′-diphenyl-2,2′-biphenolato ligand and N-N is a 1,10-phenanthroline derivative. Single-crystal analysis revealed that the neocuproine-based ligands within these architectures adopt a nonplanar geometry. The distortion of these aromatic diimine systems has been quantified through measurement of a torsion angle (α) and a dihedral angle (β) defined by two planes within the aromatic diimine molecule (π1 and π2), permitting one to evaluate the twisting and bending of a coordinated nitrogen ligand, respectively. Next, the scope of this investigation was extended to the synthesis of a dimeric architecture, [Ti2(1)4(3)], where 3 is the 5,5′-bis­(neocuproine) ligand. Again, a strong distortion of the neocuproine fragments was characterized in the crystalline state for such a complex. The UV–visible properties of these complexes were interpreted with the help of time-dependent density functional theory calculations. The solution behavior as well as good hydrolytic stability of these species has been established.