Article Dans Une Revue Inorganic Chemistry Année : 2025

Near-Infrared-Emitting Lanthanide(III)/Gallium(III) Metallacrowns with Appended Coumarins: Tuning the Sensitizer–Emitter Distance through the Linker

Résumé

Near-infrared (NIR)-emitting trivalent lanthanides (LnIII) are attractive for applications such as biological imaging and telecommunications. However, their sensitization remains challenging, particularly at excitation wavelengths corresponding to low energies. To address this challenge, a new coumarin-bearing isophthalate-based bridging ligand (C-ip2–), in which the coumarin sensitizer is directly attached to the bridge, was synthesized. In the corresponding [Ln2Ga8(shi)8(C-ip)4]2– metallacrowns (MCs), the sensitization of the NIR-emitting NdIII, ErIII, and YbIII cations was achieved upon excitation of appended coumarins in the visible range (λexc = 435 nm). Compared to the previous generation of [Ln2Ga8(shi)8(C-mip)4]2– MCs, the coumarin antennas are about 5 Å closer to the LnIII emissive centers in this new series of [Ln2Ga8(shi)8(C-ip)4]2– MCs, resulting in an increase in the Q$^{L}_{Ln}$ values by factors of 6.2, 9.4, and 2.7 for NdIII, ErIII, and YbIII analogues, respectively. This allows the detection of their NIR emissions through tissue-mimicking phantoms of 1 mm thickness, validating the potential of this design for NIR imaging applications.

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Dates et versions

hal-05362799 , version 1 (13-11-2025)
hal-05362799 , version 2 (18-11-2025)

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Timothée Lathion, Svetlana V. Eliseeva, Stéphane Petoud, Vincent L. Pecoraro. Near-Infrared-Emitting Lanthanide(III)/Gallium(III) Metallacrowns with Appended Coumarins: Tuning the Sensitizer–Emitter Distance through the Linker. Inorganic Chemistry, 2025, 64 (44), pp.22011-22020. ⟨10.1021/acs.inorgchem.5c03669⟩. ⟨hal-05362799v2⟩
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