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Article Dans Une Revue Inorganic Chemistry Frontiers Année : 2020

Peculiarities of crystal structures and photophysical properties of Ga III /Ln III metallacrowns with a non-planar [12-MC-4] core

Tu Nguyen
Svetlana Eliseeva
Chun Chow
  • Fonction : Auteur
Jeff Kampf
  • Fonction : Auteur
Stephane Petoud
Vincent Pecoraro

Résumé

A new series of gallium(iii)/lanthanide(iii) metallacrown (MC) complexes (Ln-1) was synthesized by the direct reaction of salicylhydroxamic acid (H(3)shi) with Ga-III and Ln(III) nitrates in a CH3OH/pyridine mixture. X-ray single crystal analysis revealed two types of structures depending on whether the nitrate counterion coordinate or not to the Ln(III): [LnGa(4)(shi)(4)(H(2)shi)(2)(py)(4)(NO3)](py)(2) (Ln = Gd-III, Tb-III, Dy-III, Ho-III) and [LnGa(4)(shi)(4)(H(2)shi)(2)(py)(5)](NO3)(py) (Ln = Er-III, Tm-III, Yb-III). The representative Tb-1 and Yb-1 MCs consist of a Tb/YbGa4 core with four [Ga-III-N-O] repeating units forming a non-planar ring that coordinates the central Ln(III) through the oxygen atoms of the four shi(3-) groups. Two H(2)shi(-) groups bridge the Ln(III) to the Ga-III ring ions. The Yb-III in Yb-1 is eight-coordinated while the ligation of the nine-coordinated Tb-III in Tb-1 is completed by one chelating nitrate ion. Ln-1 complexes in the solid state showed characteristic sharp f-f transitions in the visible (Tb, Dy) and near-infrared (Dy, Ho, Er, Yb) spectral ranges upon excitation into the ligand-centered electronic levels at 350 nm. Observed luminescence lifetimes and absolute quantum yields were collected and discussed. For Yb-1, luminescence data were also acquired in CH3OH and CD3OD solutions and a more extensive analysis of photophysical properties was performed. This work demonstrates that while obtaining highly luminescent lanthanide(iii) MCs via a direct synthesis is feasible, many factors such as molar absorptivities, triplet state energies, non-radiative deactivations through vibronic coupling with overtones of O-H, N-H, and C-H oscillators and crystal packing will strongly contribute to the luminescent properties and should be carefully considered.

Domaines

Chimie
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Dates et versions

hal-02935785 , version 1 (16-11-2020)

Identifiants

Citer

Tu Nguyen, Svetlana Eliseeva, Chun Chow, Jeff Kampf, Stephane Petoud, et al.. Peculiarities of crystal structures and photophysical properties of Ga III /Ln III metallacrowns with a non-planar [12-MC-4] core. Inorganic Chemistry Frontiers, 2020, 7 (7), pp.1553-1563. ⟨10.1039/c9qi01647c⟩. ⟨hal-02935785⟩
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