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Article Dans Une Revue Journal of the American Chemical Society Année : 2008

On the sensitivity of f electrons to their chemical environment.

Eric Furet
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Karine Costuas

Résumé

Density functional calculations have been carried out on three families of lanthanide complexes of D3 or C4 symmetry, namely [Ln(H2O)9]3+, [Ln(DPA)3]3-, and [Ln(DOTAM)]3+ (Ln = Y, La, Lu; DPA = pyridine-2,6-dicarboxylate; DOTAM = 1,4,7,10-tetracarbamoylmethyl-1,4,7,10-tetraazacyclododecane), to get some insights concerning the sensitivity of 4f electrons to the surrounding ligands. We show that the electron density accumulations found within 0.7 A of the metal center, that precisely give the opposite image of the coordination sphere as they are located trans with respect to the Ln-ligand bonds, are almost exclusively due the f electrons. This polarization of the 4f electrons in lanthanides complexes has therefore to be considered as a general feature that plays a crucial role in some experimentally observed phenomenons such as the dependency of quadratic hyperpolarizability to the number of f electrons in [Ln(DPA)3]3- complexes that we have evidenced.

Dates et versions

hal-00725173 , version 1 (24-08-2012)

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Eric Furet, Karine Costuas, Philippe Rabiller, Olivier Maury. On the sensitivity of f electrons to their chemical environment.. Journal of the American Chemical Society, 2008, 130 (7), pp.2180-3. ⟨10.1021/ja073224r⟩. ⟨hal-00725173⟩
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