Lanthanide Contraction within a Series of Asymmetric Dinuclear [Ln2] Complexes
作者： David Aguilà , Leoní A. Barrios , Verónica Velasco , Leticia Arnedo , Núria Aliaga-Alcalde
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摘要: A complete isostructural series of dinuclear asymmetric lanthanide complexes has been synthesized by using the ligand 6-[3-oxo-3-(2-hydroxyphenyl)propionyl]pyridine-2-carboxylic acid (H3L). All have formula [Ln2(HL)2(H2L)(NO3)(py)(H2O)] (Ln=La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9), Ho (10), Er (11), Tm (12), Yb (13), Lu (14), Y (15); py=pyridine). Complexes La to and crystallographically characterized reveal that two metal ions are encapsulated within distinct coordination environments differing size. Whereas one site maintains number (nine) through whole series, other increases from nine ten owing a change in mode an NO3− ligand. This offers unique opportunity study detail contraction more than metal. analysis shows various representative parameters proportional this follow quadratic decay as function n f electrons. Slater’s model for atomic radii used extract, these decays, shielding constant 4f The average O⋅⋅⋅O distances polyhedra shared both metals Ln⋅⋅⋅Ln separations also decay, therefore showing such dependence holds receive contribution simultaneously. magnetic behavior studied all nondiamagnetic complexes. It reveals effect spin–orbit coupling weak antiferromagnetic interaction between metals. Photoluminescent studies single broad emission band visible region, which is related coordinated On hand, Nd, Er, show features near-IR region due metal-based transitions.
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