Fully Fluorinated Imidodiphosphinate Shells for Visible‐ and NIR‐Emitting Lanthanides: Hitherto Unexpected Effects of Sensitizer Fluorination on Lanthanide Emission Properties

Glover, Peter B.; Bassett, Andrew P.; Nockemann, Peter; Kariuki, Benson M.; Deun, Rik Van; Pikramenou, Zoe

doi:10.1002/chem.200790080

Cited by 13 publications

(22 citation statements)

References 7 publications

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“…The absorption spectrum of Er(F-TPIP) 3 dissolved in DMSO exhibits two strong absorption bands with peaks at 236 and 271 nm. These bands are consistent with the absorption of F-TPIP − , and they are thus attributed to the ligand π-π* transition 25 . The energy gap of Er(F-TPIP) 3 can be determined as 4.1 eV through its absorption edge localized at 301 nm.…”

Section: Photophysical Propertiessupporting

confidence: 78%

“…Er(F-TPIP) 3 molecules have perfluorinated ligands and a large volume,~2004 Å 3 , determined from the single crystal structure. This enclosure keeps the C-H bonds on Ir-tBuPBI distant from the central Er 3+ ion to reduce vibrational quenching [23][24][25][26] . Photoexcitation gives a sensitization factor of 1600 for the Er 3+ 1.5-µm PL, two orders of magnitude larger than the best reported results for a non-halogenated phosphorescent chromophore 8 , and the longest Er 3+ NIR emission lifetime in an organic hydrogenated environment is obtained.…”

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confidence: 99%

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Enhanced 1.54-μm photo- and electroluminescence based on a perfluorinated Er(III) complex utilizing an iridium(III) complex as a sensitizer

Liu

Lyu

et al. 2020

Light Sci Appl

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Advanced 1.5-µm emitting materials that can be used to fabricate electrically driven light-emitting devices have the potential for developing cost-effective light sources for integrated silicon photonics. Sensitized erbium (Er 3+) in organic materials can give bright 1.5-µm luminescence and provide a route for realizing 1.5-µm organic light emitting diodes (OLEDs). However, the Er 3+ electroluminescence (EL) intensity needs to be further improved for device applications. Herein, an efficient 1.5-µm OLED made from a sensitized organic Er 3+ co-doped system is realized, where a "traditional" organic phosphorescent molecule with minimal triplet-triplet annihilation is used as a chromophore sensitizer. The chromophore provides efficient sensitization to a co-doped organic Er 3+ complex with a perfluorinatedligand shell. The large volume can protect the Er 3+ 1.5-µm luminescence from vibrational quenching. The average lifetime of the sensitized Er 3+ 1.5-µm luminescence reaches~0.86 ms, with a lifetime component of 2.65 ms, which is by far the longest Er 3+ lifetime in a hydrogen-abundant organic environment and can even compete with that obtained in the fully fluorinated organic Er 3+ system. The optimal sensitization enhances the Er 3+ luminescence by a factor of 1600 even with a high concentration of the phosphorescent molecule, and bright 1.5-µm OLEDs are obtained.

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Section: Photophysical Propertiessupporting

confidence: 78%

mentioning

confidence: 99%

Enhanced 1.54-μm photo- and electroluminescence based on a perfluorinated Er(III) complex utilizing an iridium(III) complex as a sensitizer

Liu

Lyu

et al. 2020

Light Sci Appl

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“…More important, this result was obtained in solid state, which is more than 2 times bigger than previous one in the similar conditions for this complex. [5] With such result for NIR-emitting ions, the development of an upconversion system is a logical step forward. Fig.…”

Section: Hf-tpip -Ultimate Ligand For Nir Emissionmentioning

confidence: 99%

“…[5] ~13 ppm difference in 31 P shift for Tb(F-TPIP) 3 can be attributed to the differences in solvent coordination to lanthanide which is known to happen for Tb(F-TPIP) 3 . [5] For all of the complexes the signal of p-ArCF can be used as an analytical signal for confirming the ratio between lanthanide complexes in mixed materials. The ratio of the signals was found to be consistent (±10 %) with the ratio of the lanthanide chlorides used in the synthesis thus confirming the proportions of the lanthanide ions in the studied materials.…”

Section: Materials Synthesis and Characterizationmentioning

confidence: 99%

“…Reasonably high luminescent quantum yields for Er 3+ (~7%) and Yb 3+ (~50%) were achieved for the fully fluorinated complex with N-{P,P-di(pentafluorophinoyl)}-P,P-dipentafluorophenylphosphinimidate (HF-TPIP, Fig. 1) as a ligand [4], [5], while other works, even that claim the synthesis of "highly luminescent" complexes, report the luminescent lifetimes of Yb 3+ only of 10-20 µs which corresponds to <2% QY. [6], [7] Recently published research provides another perspective ligand for Yb 3+ NIR emission, however, its structure is more complicated compared to F-TPIP and the improvement in the internal quantum yield (63%) is achievable in the environment of hydrogen-free solvent, which is not seriously significant.…”

Section: Introductionmentioning

confidence: 99%

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Fluorinated lanthanide complexes : new NIR-VIS upconversion systems

Bogdanov¹

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Lanthanide-based upconversion is a well-known process in solids, but for a wide variety of applications small size, preferentially molecular size upconversion emitters are required. Using inorganic upconversion nanoparticles solves some of the problems, however, the luminescence is severely quenched for smaller particle sizes. On the other hand, organic lanthanide complexes provide better overall luminosities and can be easily modified for medical applications, but rarely provide adequate quantum yield of NIR emission to enable upconversion processes. This work was aimed to realize conventional for inorganic systems Yb-Tb/Er upconversion in the perfluorinated organic complex and study its mechanism in order to explore the limits of the system and evaluate the perspective pathway. Green Yb-Tb upconversion by cooperative energy transfer (CET) mechanism was realized in vacuum, and green/red Yb-Er upconversion by energy transfer (ETU) mechanism was shown to be possible in ambient conditions for organic complex powder. Energy transfer pathways were studied in detail to explain features of the mechanisms, such as three-photon red upconversion for the latter case. Based on this data the conclusion about the perspectives is drawn and the outlook of the future work in the field is provided.

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Dichalcogenoimidodiphosph(in)ate Ligands

Haiduc

2013

Reference Module in Chemistry, Molecular Sciences and Chemical Engineering

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Fully Fluorinated Imidodiphosphinate Shells for Visible‐ and NIR‐Emitting Lanthanides: Hitherto Unexpected Effects of Sensitizer Fluorination on Lanthanide Emission Properties

Cited by 13 publications

References 7 publications

Enhanced 1.54-μm photo- and electroluminescence based on a perfluorinated Er(III) complex utilizing an iridium(III) complex as a sensitizer

Enhanced 1.54-μm photo- and electroluminescence based on a perfluorinated Er(III) complex utilizing an iridium(III) complex as a sensitizer

Fluorinated lanthanide complexes : new NIR-VIS upconversion systems

Dichalcogenoimidodiphosph(in)ate Ligands

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