Room temperature molecular up conversion in solution

Nonat, Aline; Chan, Chi Fai; Liu, Tao; Platas‐Iglesias, Carlos; Liu, Zhenyu; Wong, Wing Tak; Wong, Wai Kwok; Wong, Ka Leung; Charbonnière, Loı̈c J.

doi:10.1038/ncomms11978

Cited by 91 publications

(88 citation statements)

References 44 publications

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“…Upconversion was long restricted to inorganic systems, but in 2011 molecular upconversion was demonstrated in a trinuclear, bimetallic ErCrEr helicate in the solid state . Expansion to solutions is now established, and there is hope that applications to biosciences will follow suit.…”

Section: Applicationsmentioning

confidence: 99%

Rising Stars in Science and Technology: Luminescent Lanthanide Materials

Bünzli

2017

Eur J Inorg Chem

157

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This essay draws attention to lanthanide luminescence by putting into perspective the sensitization process of f-f emission, the design of highly luminescent lanthanide-based compounds, and upconversion nanoparticles. A brief overviewLanthanide luminescence is at the heart of applications as diverse as lighting, telecommunications, displays, lasers, security inks and marking, pressure sensors, barcoding, molecular thermometers, immunoassays, and bioimaging ( Figure 1). The phenomenon is fascinating and has constantly accompanied the development of lanthanide science and technology, from the early discovery of the 4f elements to the present high-technology applications. Lanthanide-containing light-emitting materials (phosphors and pigments) represent the second most important application of rare earths with respect to the commercial value of the oxides needed for their production, just behind magnets. However, tonnage-wise these materials represent a rather small share of the total rare earths used annually, about 4 %. In addition to the fascination for light emission, this large added value explains the enthusiasm research groups have in looking for new and better luminescent materials.Most lanthanide ions are luminescent, and the corresponding transitions occur either as allowed d-f transitions or as electronic rearrangements within the 4f shell (f-f transitions). Interconfigurational d-f transitions are more energetic and more intense than f-f transitions but are observed in the common UV/visible spectroscopic range only for Ce III , Pr III , Tb III , and some Ln II ions (Ln = Sm, Eu, Tm, Yb). Electric-dipole (ed) f-f transitions are forbidden by Laporte's selection rule, while magnetic-dipole [a]

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Section: Applicationsmentioning

confidence: 99%

Rising Stars in Science and Technology: Luminescent Lanthanide Materials

Bünzli

2017

Eur J Inorg Chem

157

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“…To the best of our knowledge, the unambiguous implementation of ESA in molecular complexes under reasonable incident pump intensities (i.e., below 1 kW cm −2 ) is currently unknown, and the few successful molecular erbium‐centered upconverters reported so far exploit the ETU mechanism as found in [IR‐806][Er(tta) 4 ] (use of a polyaromatic sensitizer), [CrErCr( L1 ) 3 ] 9+ (use of a d‐block sensitizer), [( L2 Er)F(Er L2 )] + , and [YbEr( L3 ) 6 (DME) 2 ] (use of f‐block sensitizers, Scheme ) . Beyond some classical optimization of the sensitization in the latter complexes maximizing NIR absorption cross sections, the ultimate induction of visible Er‐centered emission, for instance, the green Er( 4 S 3/2 → 4 I 15/2 ) signal, while at least one long‐lived intermediate excited state relay of lower energy is available, for instance Er( 4 I 13/2 ), represents a major impediment for the implementation of successful linear piling up of photons in these molecular systems.…”

Section: Introductionmentioning

confidence: 99%

Thermodynamic Programming of Erbium(III) Coordination Complexes for Dual Visible/Near‐Infrared Luminescence

Golesorkhi

Guénée

Nozary

et al. 2018

Chemistry A European J

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Intrigued by the unexpected room-temperature dual visible/near-infrared (NIR) luminescence observed for fast-relaxing erbium complexes embedded in triple-stranded helicates, in this contribution, we explore a series of six tridentate N-donor receptors L4-L9 with variable aromaticities and alkyl substituents to extricate the stereoelectronic features responsible for such scarce optical signatures. Detailed solid-state (X-ray diffraction, differential scanning calorimetry, optical spectroscopy) and solution (speciations and thermodynamic stabilities, spectrophotometry, NMR and optical spectroscopy) studies of mononuclear unsaturated [Er(Lk) ] and saturated triple-helical [Er(Lk) ] model complexes reveal that the stereoelectronic changes induced by the organic ligands affect inter- and intramolecular interactions to such an extent that 1) melting temperatures in solids, 2) the affinity for trivalent erbium in solution, and 3) optical properties in luminescent complexes can be rationally varied and controlled. With this toolkit in hand, mononuclear erbium complexes with low stabilities displaying only NIR emission can be transformed into molecular-based dual Er-centered visible/NIR emitters operating at room temperature in both solid and solution states.

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“…Very recently, we demonstrated that this strategy could be further extended to heavy water, with the observation of UC in a supramolecular Er dimer or heteropolynuclear Tb/Yb species . Herein, the factors that govern the supramolecular assembly of the Er dimer were investigated thanks to the solid‐state structures of the monomeric and fluoride‐bridged dimeric complexes of the analogous Yb cations.…”

Section: Introductionmentioning

confidence: 99%

Energy Transfer in Supramolecular Heteronuclear Lanthanide Dimers and Application to Fluoride Sensing in Water

Nonat

Liu

Jeannin

et al. 2018

Chemistry A European J

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In the presence of fluoride anions, [LnL(H O)] complexes, based on the coordination of a lanthanide (Ln) cation into the cavity of a C symmetrical cyclen-based ligand (L), self-assemble in water to form [(LnL) F] dimers. The crystal structures of the Yb hydrated monomer and of the fluorinated dimer are reported and analyzed to unravel the impact of the cumulative effect of weak hydrogen bonding and aromatic stacking interactions in the supramolecular assembly. The assembly is stable over a broad range of pH 3-8. A combination of equimolar amounts of Eu and Tb complexes led to a quasistatistical mixture of homo- and heterodimers, as observed by using electrospray mass spectrometry. In the heterodimers, selective excitation into the F → D absorption band of the Tb center at λ=488 nm allowed the observation of a Tb-to-Eu downshifting energy transfer, not observed in the absence of fluoride ions. Analysis of the excited-state lifetimes of the dimers within the frame of the Förster theory of energy transfer showed the transfer to have an efficiency of 34 %, with a corresponding Förster radius of 4.1 Å; thereby, unraveling the short Ln-Ln distance as a crucial parameter of the energy-transfer process. By using equimolar mixtures of the Tb and Eu complexes, the energy-transfer phenomenon was used for a ratiometric sensing of fluoride anions in water with a detection limit of 17.7 nm.

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Room temperature molecular up conversion in solution

Cited by 91 publications

References 44 publications

Rising Stars in Science and Technology: Luminescent Lanthanide Materials

Rising Stars in Science and Technology: Luminescent Lanthanide Materials

Thermodynamic Programming of Erbium(III) Coordination Complexes for Dual Visible/Near‐Infrared Luminescence

Energy Transfer in Supramolecular Heteronuclear Lanthanide Dimers and Application to Fluoride Sensing in Water

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