We report here the characterization in solution (NMR, luminescence, MS) and the solid-state (X-ray crystallography, IR) of complexes between phenacyldiphenylphosphine oxide and five Ln( iii ) ions (Sm, Eu, Gd, Tb, Dy). Four single crystal X-ray structures are described here showing a 1 : 2 ratio between the Ln 3+ ions Eu, Dy, Sm and Gd and the ligand, where the phosphine oxide ligands are bound in a monodentate manner to the metal center. A fifth structure is reported for the 1 : 2 Eu(NO 3 ) 3 -ligand complex showing bidentate binding between the two ligands and the metal center. The solution coordination chemistry of these metal complexes was probed by 1 H, 13 C and 31 P NMR, mass spectrometry, and luminescence experiments. The title ligand has the capability to sensitize Tb 3+ , Dy 3+ , Eu 3+ and Sm 3+ leading to metal-centered emission in solutions of acetonitrile and methanol and in the solid state.
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Synthesis of diphenyl-(2-thienyl)phosphine, its chalcogenide derivatives and a series of novel complexes of lanthanide nitrates and triflates
A novel synthesis of diphenyl(2-thienyl)phosphine, along with its’ oxide, sulfide and selenide derivatives, is reported here. These phosphines have been characterized by NMR, IR, MS and X-Ray crystallography. The phosphine oxide derivative was reacted with a selection of lanthanide( iii ) nitrates and triflates, LnX 3 , to give the resultant metal–ligand complexes. These complexes have also been characterized by NMR, IR, MS and X-Ray crystallography. Single crystal X-Ray diffraction data shows a difference in metal–ligand complex stoichiometry and stereochemistry depending on the counteranion (nitrate vs. triflate). The [Ln(Ar 3 PO) 3 (NO 3 ) 3 ] ligand–nitrate complexes are nine-coordinate to the metal in the solid state (bidentate nitrate), featuring a 1 : 3 lanthanide–ligand ratio and bear an overall octahedral arrangement of the six, coordinated ligands. Our [Ln(Ar 3 PO) 3 (NO 3 ) 3 ] ligand–nitrate complexes gave three examples of fac -stereochemistry, where mer -stereochemistry is almost universally observed in the literature of highly related [Ln(Ar 3 PO) 3 (NO 3 ) 3 ] complexes. For the Tb complexes, two different arrangements of the ligands around the metal were observed in the solid state for [Tb(Ar 3 PO) 3 (NO 3 ) 3 ] and [Tb(Ar 3 PO) 4 (OTf) 2 ] [OTf]. [Tb(Ar 3 PO) 3 (NO 3 ) 3 ] is strictly nine-coordinate, ligand mer -stereochemistry in the solid state, and [Tb(Ar 3 PO) 4 (OTf) 2 ] [OTf] is strictly octahedral, six-coordinate, with a square-planar stereochemical arrangement of the phosphine oxide ligands around the metal.
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- NSF-PAR ID:
- 10333384
- Date Published:
- Journal Name:
- Dalton Transactions
- Volume:
- 51
- Issue:
- 23
- ISSN:
- 1477-9226
- Page Range / eLocation ID:
- 9103 to 9115
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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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.more » « less
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d2dt01570f
