Ga$^{3+}$/Ln$^{3+}$ metallacrowns: a promising family of highly luminescent lanthanide complexes that covers visible and near-infrared domains - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of the American Chemical Society Année : 2016

Ga$^{3+}$/Ln$^{3+}$ metallacrowns: a promising family of highly luminescent lanthanide complexes that covers visible and near-infrared domains

Résumé

Luminescent lanthanide(III)-based molecular scaffolds hold great promises for materials science and for biological applications. Their fascinating photophysical properties enable spectral discrimination of emission bands that range from the visible to the near-infrared (NIR) regions. In addition, their strong resistance to photobleaching makes them suitable for long duration or repeated biological experiments using a broad range of sources of excitation including intense and focalized systems such as lasers (e.g., confocal microscopy). A main challenge in the creation of luminescent lanthanide(III) complexes lies in the design of a ligand framework that combines two main features: (i) it must include a chromophoric moiety that possesses a large molar absorptivity and is able to sensitize several different lanthanide(III) ions emitting in the visible and/or in the near-infrared, and (ii) it must protect the Ln3+ cation by minimizing nonradiative deactivation pathways due to the presence of −OH, −NH and −CH vibrations. Herein, a new family of luminescent Ga$^{3+}$/Ln$^{3+}$ metallacrown (MC) complexes is reported. The MCs with the general composition [LnGa$_4$(shi)$_4$(C$_6$H5CO$_2$)$_4$(C$_5$H$_5$N) (CH$_3$OH)] ($Ln-1$, Ln = Sm$^{3+}$–Yb$^{3+}$) were synthesized in a one pot reaction using salicylhydroxamic acid (H$_3$shi) with Ga$^{3+}$ and Ln$^{3+}$ nitrates as reagents. The molecular structure of [DyGa$_4$(shi)$_4$(C$_6$H$_5$CO$_2$)$_4$(C$_5$H$_5$N) (CH$_3$OH)] was obtained by X-ray analysis of single crystals and shows that the complex is formed as a [12-MC$_{Ga(III)shi}$-4] core with four benzoate molecules bridging the central Dy$^{3+}$ ion to the Ga$^{3+}$ ring metals. The powder X-ray diffraction analysis demonstrates that all other isolated complexes are isostructural. The extended analysis of the luminescence properties of these complexes, excited by the electronic states of the chromophoric ligands, showed the presence of characteristic, sharp f–f transitions that can be generated not only in the NIR (Sm, Dy, Ho, Er, Yb) but also in the visible (Sm, Eu, Tb, Dy, Tm). All Ln-1 complexes possess very high quantum yield values with respect to other literature compounds, indicating a good sensitization efficiency of the [12-MC$_{Ga(III)shi}$-4] scaffold. Especially, as of today, the $Yb-1$ complex exhibits the highest NIR quantum yield reported for a lanthanide(III) complex containing C–H bonds with a value of 5.88(2)% in the solid state. This work is a significant step forward toward versatile, easily prepared luminescent lanthanide(III) complexes suitable for a variety of applications including highly in demand biological imaging, especially in the NIR domain.
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Dates et versions

hal-01406887 , version 1 (01-12-2016)

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Chun Y. Chow, Svetlana V. Eliseeva, Evan R. Trivedi, Tu N. Nguyen, Jeff W. Kampf, et al.. Ga$^{3+}$/Ln$^{3+}$ metallacrowns: a promising family of highly luminescent lanthanide complexes that covers visible and near-infrared domains. Journal of the American Chemical Society, 2016, 138 (15), pp.5100 - 5109. ⟨10.1021/jacs.6b00984⟩. ⟨hal-01406887⟩
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