A Single Sensitizer for the Excitation of Visible and NIR Lanthanide Emitters in Water with High Quantum Yields

Law, Ga‐Lai; Pham, Tiffany A.; Xu, Jide; Raymond, Kenneth N.

doi:10.1002/ange.201106748

Cited by 20 publications

(4 citation statements)

References 35 publications

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“…8 In the case of the Tb(tpOp) 3 , the high quantum yield is comparable to those reported for the cryptate-based complexes 36,37 and octadentate ligands in aqueous media. 38 This could be due to the efficient transfer between the lower lying energy state in the Tb(tpOp) 3 complex and the terbium emissive state.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Imidodiphosphonate Ligands for Enhanced Sensitization and Shielding of Visible and Near-Infrared Lanthanides

et al. 2019

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The design of coordination sites around lanthanide ions has a strong impact on the sensitization of their luminescent signal. An imidodiphosphonate anionic binding site is attractive as it can be functionalized with "remote" sensitizer units, such as phenoxy moieties, namely, HtpOp, accompanied by an increased distance of the lanthanide from the ligand high-energy stretching vibrations which quench the luminescence signal, hence providing flexible shielding of the lanthanide. We report the formation and isolation of Ln(tpOp)3 complexes where Ln = Er, Gd, Tb, Dy, Eu, and Yb and the Y(tpOp)3 diamagnetic analogue. The complexes are formed from reaction of KtpOp and the corresponding LnCl3•6H2O salt either by titration and in situ formation or by mixing and isolation. All complexes are seven-coordinated by three tpOp ligand plus one ethanol molecule, except for Yb(tpOp)3 which has no solvent coordinated. Phosphorus NMR shows characteristic shifts to support the coordination of the lanthanide complexes. The complexes display visible and near-infrared luminescence with long lifetimes even for the near-infrared complexes which range from 3.3 μs for Nd(tpOp)3 to 20 μs for Yb(tpOp)3. The ligand shows more efficient sensitization than the imidodiphosphinate analogues for all lanthanide complexes with a notable quantum yield of the Tb(tpOp)3 complex at 45%. We attribute this to the properties of the remote sensitizer unit and its positioning further away from the lanthanide, eliminating quenching of high energy C−H vibrations from the ligand shell. Calculations of the ligand shielding support the photophysical properties of the complexes. These results suggest that these binding sites are promising in the further development of the lanthanide complexes in optoelectronic devices for telecommunications and new light emitting materials.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Imidodiphosphonate Ligands for Enhanced Sensitization and Shielding of Visible and Near-Infrared Lanthanides

et al. 2019

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“…There are only a few examples of ligands able to sensitize all emitting Ln ions like Cum does. − This is rather notable because crystal structures show two OH groups directly bonded to the metal ion, one from a water molecule and another from EtOH or MeOH, which are known to quench Ln emissions. As can be appreciated in Figure , for the Pr, Nd, Ho, Er, Tm, and Yb complexes, commonly reported emissions become clearly visible, but the ligand-centered emission is a prominent feature in the spectra.…”

mentioning

confidence: 99%

Coumarin Derivative Directly Coordinated to Lanthanides Acts as an Excellent Antenna for UV–Vis and Near-IR Emission

Guzmán-Méndez

González²,

Bernès

et al. 2018

Inorg. Chem.

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“…Moreover, the emission lines of the rare-earth metals are sharp because the excitation of an electron into a 4f orbital of higher energy is almost not influenced by the ligands in a metal complex. Most work that has been published in the area of luminescent rare-earth metal complexes deals with Eu(III) and Tb(III) because the excited states of these ions are less sensitive to vibrational quenching by intra- or intermolecular energy transfer to adjacent high-energy vibrators such as hydroxyl groups . The advantage of using mononuclear rare-earth metal complexes as cellular probes in general is their rational design. , However, the susceptibility of rare-earth metal and in particular lanthanide(III) (Ln(III)) ion luminescence to quenching effects caused by water or hydroxyl groups is a drawback of such mononuclear complexes .…”

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confidence: 99%

Luminescent Cell-Penetrating Pentadecanuclear Lanthanide Clusters

Thielemann¹,

Wagner²,

Rösch³

et al. 2013

J. Am. Chem. Soc.

115

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A novel pentadecanuclear lanthanide hydroxy cluster [{Ln15(μ3-OH)20(PepCO2)10(DBM)10Cl}Cl4] (Ln = Eu (1), Tb (2)) featuring the first example with peptoids as supporting ligands was prepared and fully characterized. The solid-state structures of 1 and 2 were established via single-crystal X-ray crystallography. ESI-MS experiments revealed the retention of the cluster core in solution. Although OH groups are present, 1 showed intense red fluorescence with 11(1)% absolute quantum yield, whereas the emission intensity and the quantum yield of 2 were significantly weaker. In vitro investigations on 1 and 2 with HeLa tumor cells revealed an accumulation of the clusters in the endosomal-lyosomal system, as confirmed by confocal microscopy in the TRLLM mode. The cytotoxicity of 1 and 2 toward the HeLa cells is moderate.

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A Single Sensitizer for the Excitation of Visible and NIR Lanthanide Emitters in Water with High Quantum Yields

Cited by 20 publications

References 35 publications

Imidodiphosphonate Ligands for Enhanced Sensitization and Shielding of Visible and Near-Infrared Lanthanides

Imidodiphosphonate Ligands for Enhanced Sensitization and Shielding of Visible and Near-Infrared Lanthanides

Coumarin Derivative Directly Coordinated to Lanthanides Acts as an Excellent Antenna for UV–Vis and Near-IR Emission

Luminescent Cell-Penetrating Pentadecanuclear Lanthanide Clusters

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