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 CH 3 OH/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 (NO 3 )](py) 2 (Ln = Gd III , Tb III , Dy III , Ho III ) and [LnGa 4 (shi) 4 (H 2 shi) 2 (py) 5 ](NO 3 )(py) (Ln = Er III , Tm III , Yb III ). The representative Tb-1 and Yb-1 MCs consist of a Tb/YbGa 4 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 CH 3 OH and CD 3 OD 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.
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Synthesis of bright water-soluble circularly polarized luminescence emitters as potential sensors
We describe the synthesis of C 2 -symmetrical enantiopure lanthanide complexes (Tb, Eu, Sm, Dy) supported by the decadentate ligand N , N , N ′, N ′-tetrakis[(6-carboxypyridin-2-yl)methyl]-1,2-diaminocyclohexane (tpadac). The chiral tpadac ligand was designed to protect the lanthanide center from coordination of inner-sphere water molecules resulting in air- and water-stable, and highly luminescent complexes in water. The complexes exhibit strong chiroptical properties, with high dissymmetry factors g lum (0.11 to 0.25) and CPL brightness B CPL (up to 245 M −1 cm −1 for Tb, λ exc 295 nm, λ em 544 nm) in water. These are the first example of aqueous Sm CPL and second example of aqueous Dy CPL reported to date. The lanthanide complexes obtained gave a reversible CPL response to pH ranging from 6.0 to 8.0. In addition, distinctive CPL responses (including a change in CPL sign) towards toxic cations (Pb 2+ , Cd 2+ , and Mn 2+ ) were also observed, demonstrating the potential of our complexes to be used as aqueous probes.
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- Award ID(s):
- 2041084
- NSF-PAR ID:
- 10351482
- Date Published:
- Journal Name:
- Inorganic Chemistry Frontiers
- Volume:
- 9
- Issue:
- 7
- ISSN:
- 2052-1553
- Page Range / eLocation ID:
- 1474 to 1480
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D1QI01398J
