Formation of Mono- and Polynuclear Luminescent Lanthanide Complexes based on the Coordination of Preorganized Phosphonated Pyridines

Salaam, Jeremy; Tabti, Lilia; Bahamyirou, Sylvana; Lecointre, Alexandre; Alba, Oscar Hernandez; Jeannin, Olivier; Camerel, Franck; Cianférani, Sarah; Bentouhami, Embarek; Nonat, Aline; Charbonnière, Loı̈c J.

doi:10.1021/acs.inorgchem.8b00666

Cited by 24 publications

(32 citation statements)

References 57 publications

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“…Starting from the commercially available 2‐chloromethyl‐pyridine 1 , N‐oxidation using m ‐CPBA in chloroform afforded the corresponding pyridine‐ N ‐oxyde, which is functionalized into the o ‐phosphonic ethyl ester 2 by reaction with ethyl chloroformate and triethyl phosphite according to literature procedures . The formation of the tripod was achieved in 42 % yield by adaptation of a procedure developed by Mikata and co‐workers using acetaldehyde ammonia trimer .…”

Section: Resultsmentioning

confidence: 99%

“…The given pH values are corrected for the deuterium isotopic effects (pD = apparent pH + 0.4) . Compound 2 was obtained according to literature procedures …”

Section: Methodsmentioning

confidence: 99%

“…The presence of numerous phosphonate functions resulted in potentially large negative charges on the complexes, which may interact with additional Ln 3+ cations in the solution to form polynuclear species. In view of recent results on polyphosphonated Ln complexes integrating other analyticals tools such as mass spectrometry,, it appears that the composition of such adducts can be even larger with the potential formation of tri‐ to pentanuclear species, the composition of which can be adjusted to obtained pure heteropolynuclear species with exceptional spectroscopic properties such as molecular upconversion in heavy water and more recently in pure water …”

Section: Introductionmentioning

confidence: 99%

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Phosphonated Podand Type Ligand for the Complexation of Lanthanide CationsPhosphonated Podand Type Ligand for the Complexation of Lanthanide Cations

et al. 2019

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A new tripodal ligand, based on a central nitrogen atom tris‐functionalized with 6‐methylene‐2‐pyridyl phosphonic acid was synthesized and characterized, in particular by its X‐ray crystal structure. The coordination behaviour of the tripod with lanthanide cations in aqueous solutions was studied by means of UV/Vis electronic absorption spectroscopy and steady‐state and time‐resolved luminescence spectroscopy, revealing the formation of a [LnL] complex followed by polynuclear species with 2:1 and 3:1 metal/ligand stoichiometries. The [LnL] complexes (Ln = Eu, Tb and Yb) were isolated and characterized and the solid‐state structure of the Eu complex was determined by X‐ray diffraction analysis on monocrystals, revealing the observation of dimeric species, in which the Ln3+ cations are firmly held in the cavity formed by the three pyridylphosphonate arms, the coordination of the cations being completed by a water molecule and a phosphonate function of the second complex, allowing for the formation of the dimers, which are further stabilized by π–π stacking interactions between one pyridyl unit of each adjacent monomer. The spectroscopic properties of the complexes in aqueous solutions were studied, showing an impressive 16 µs excited state lifetime for the Yb complex in D2O, despite the presence of a water molecule in the first coordination sphere.

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Section: Resultsmentioning

confidence: 99%

“…The given pH values are corrected for the deuterium isotopic effects (pD = apparent pH + 0.4) . Compound 2 was obtained according to literature procedures …”

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Phosphonated Podand Type Ligand for the Complexation of Lanthanide CationsPhosphonated Podand Type Ligand for the Complexation of Lanthanide Cations

et al. 2019

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“…The promising structural and photophysical properties highlighted above, coupled with prior precedent of formation of polyatomic species in aqueous solutions, 47,48,54,55 should facilitate the formation of higher order polynuclear complexes in solution. To study these properties, a 1 H NMR investigation (298K, D2O, pD = 6.5 -7.0) was conducted, in which the lutetium complex [LuL1]was titrated with increasing amounts of LuCl3 (Figure 7).…”

Section: Solution and Spectroscopic Studies Of Heteropolynuclear Assementioning

confidence: 99%

Formation of Heteropolynuclear Lanthanide Complexes Using Macrocyclic Phosphonated Cyclam-Based Ligands

et al. 2020

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Ligands L1 and L2, respectively based on a cyclam and a cross-bridged cyclam scaffold functionalised at N1 and N8 by 6-phosphonic-2-methylene pyridyl groups are described. While 2 complexation of lanthanide (Ln) cations with L2 was not possible, a family of complexes has been prepared with L1, of the general formulae [LnL1D2]Cl (Ln 3+ = Lu, Tb, Yb) or [LnL1D] (Ln 3+ = Eu). The solution, structural, potentiometric and photophysical data for these novel ligands and their complexes have been investigated, including solid-state study by X-ray diffraction (L1, L2 and [EuL1H]), 1 H NMR complexation investigations (Lu 3+) as well as UV-Vis absorption and luminescence spectroscopy in water and D2O (pH ≈ 7). L1 forms 1:1 metal-ligand stoichiometric octadentate complexes in solution. Importantly the pyridyl phosphonate functions are capable of simultaneous chelation to the metal centre and of interaction with a second metal centre. 1 H NMR (Lu 3+) and spectrophotometric titrations of the isolated [TbL1]complex by EuCl3 salts demonstrated the formation of high order (hetero)polymetallic species in aqueous solution (H2O, pH = 7). Global analysis of the luminescence titration experiment points to the formation of 4:1, 3:1, and 3:2 [TbL1]:Eu heteropolynuclear assemblies, exhibiting a strong preference to forming [TbL1]3Eu2 at increased europium concentrations, with energy transfer occurring between the kinetically inert terbium complex and added europium cations.

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“…It was fantastic to find that, via the efficient Ir→Eu→Yb cascade ET process, the longest decay lifetime of 553 μs could be achieved for the Yb 3+ -based DCL-NIR in Ir-Eu 0.75 Yb 0.25 complex, which is amongst the topmost in ever-reported Yb-complexes at such ambient conditions of RT and in the solid-state. [27][28][29][30]…”

Section: Nir-dcl Emission Via Ir→eu→yb Energy Transfer Cascadementioning

confidence: 99%

Highly Efficient DCL, UCL, and TPEF in Hybridized Ln-Complexes from Ir-Metalloligand

Zheng

et al. 2021

CCS Chem

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In molecular level lanthanide complexes, it is still challenging to achieve near-infrared (NIR) down-conversion luminescence (DCL) and visible up-conversion luminescence (UCL) efficiently under ambient conditions. By delicate design of hybridized iridium−europium−ytterbium (Ir-Eu-Yb) trimetallic complexes from an Ir-metalloligand, DCL and UCL emissions with opposite photon conversion pathways were achieved simultaneously in one integrated system. In detail, three different types of energy transfer (ET) and photoluminescence (PL) were detected, as follows: (1) Highly sensitized NIR-DCL from Yb(III) center via ET Ir→Eu→Yb , which gave the longest decay lifetime (553 μs) at room temperature ever reported in solid-state Yb-complexes. (2) Unprecedented UCL red emission from Eu(III) center via ET Yb→Eu using 980 nm continuous wavelength (CW) laser excitation, which required ultralow energy threshold (0.616 W/cm 2 ). (3) Two-photon excited fluorescence (TPEF) via ET Ir→Eu using femtosecond pulsed laser excitation. This exquisite module of "one stone, three birds" provides a new stimulus in the design and application of multifunctional UCL/DCL/ TPEF optical materials under ambient conditions.

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Formation of Mono- and Polynuclear Luminescent Lanthanide Complexes based on the Coordination of Preorganized Phosphonated Pyridines

Cited by 24 publications

References 57 publications

Phosphonated Podand Type Ligand for the Complexation of Lanthanide CationsPhosphonated Podand Type Ligand for the Complexation of Lanthanide Cations

Phosphonated Podand Type Ligand for the Complexation of Lanthanide CationsPhosphonated Podand Type Ligand for the Complexation of Lanthanide Cations

Formation of Heteropolynuclear Lanthanide Complexes Using Macrocyclic Phosphonated Cyclam-Based Ligands

Highly Efficient DCL, UCL, and TPEF in Hybridized Ln-Complexes from Ir-Metalloligand

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