A convenient synthesis of highly luminescent lanthanide 1D-zigzag coordination chains based only on 4,4′-bipyridine as connector

Armelao, Lidia; Dell’Amico, Daniela Belli; Bellucci, Luca; Bottaro, Gregorio; Labella, Luca; Marchetti, Fabio; Samaritani, Simona

doi:10.1016/j.poly.2016.09.009

Cited by 19 publications

(20 citation statements)

References 65 publications

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“…In our previous work, we carefully described the synthesis of monodimensional lanthanide β-diketonate coordination polymers based on bipy as connector ligand [ 33 ]. The synthesis of these CPs must be carried out in anhydrous toluene, avoiding the use of oxygenated solvents.…”

Section: Resultsmentioning

confidence: 99%

“…Anhydrous toluene was purchased from Merck and used without further purification. [Eu(hfac) 3 ] and [Tb(hfac) 3 ] were prepared from the corresponding bi-hydrated complex [Ln(hfac) 3 (H 2 O) 2 ] according to the literature [ 33 ]. 4,4′-bipyridine (bipy, Aldrich) was used as received.…”

Section: Methodsmentioning

confidence: 99%

“…Recently, we developed a convenient strategy for the synthesis of a series of highly luminescent one-dimensional lanthanide zigzag polymeric chains with composition [Ln(β-dike) 3 (bipy)] n based on lanthanide tris -β-diketonato complexes as nodes (for Ln 3+ = Eu 3+ and Tb 3+ ; β-dike = dibenzoylmethide, dbm; while for Ln 3+ = Eu 3+ β-dike = thenoyltrifluoroacetonate, tta, or hexafluoroacetilacetonate, hfac) and 4,4′-bipyridine (bipy) as neutral spacer [ 33 , 34 ]. To develop a heterometallic ratiometric thermometer, the “ antenna ligand ”, i.e., the organic molecule that sensitizes lanthanide emission [ 35 , 36 ], must have a triplet energy level high enough to promote the indirect excitation of both lanthanides ions.…”

Section: Introductionmentioning

confidence: 99%

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1D-Zigzag Eu3+/Tb3+ Coordination Chains as Luminescent Ratiometric Thermometers Endowed with Multicolor Emission

et al. 2021

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Two homometallic Coordination Polymers (CPs) with composition [Ln(hfac)3bipy]n (Ln3+ = Eu3+, 1, and Tb3+, 2; hfac = hexafluoroacetylacetonato, bipy = 4,4′-bipyridine) were used to develop a family of ratiometric luminescent thermometers containing Eu3+ and Tb3+ as red and green emitters, respectively. The thermometric properties of pure CPs and of their mixtures having an Eu3+/Tb3+ molar ratio of 1:1, 1:3, 1:5, and 1:10 (samples: Eu1Tb1, Eu1Tb3, Eu1Tb5, and Eu1Tb10) were studied in the 83–383 K temperature range. Irrespective of the chemical composition, we observed similar thermometric responses characterized by broad applicative temperature ranges (from 100 to 165 K wide), and high relative thermal sensitivity values (Sr), up to 2.40% K−1, in the physiological temperature range (298–318 K). All samples showed emissions endowed with peculiar and continuous color variation from green (83 K) to red (383 K) that can be exploited to develop a colorimetric temperature indicator. At fixed temperature, the color of the emitted light can be tuned by varying composition and excitation wavelength.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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1D-Zigzag Eu3+/Tb3+ Coordination Chains as Luminescent Ratiometric Thermometers Endowed with Multicolor Emission

et al. 2021

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“…Therefore, with all the diketonates we used, the assemblage of [Ln(β‐dik) 3 ] with bipyMO proceeds with formation of dinuclear molecules where only the oxygen atom of the divergent ligand is engaged in the coordination to the metal ion. With bipyMO ligands, nitrogen functionalities do not appear able to coordinate the lanthanide metal, although bipy has been used as exclusive spacer in 1D polymers having neutral lanthanide diketonate complexes as nodes …”

Section: Resultsmentioning

confidence: 99%

Homodinuclear Lanthanide Complexes with the Divergent Heterotopic 4,4′‐Bipyridine N‐Oxide (bipyMO) Ligand

et al. 2018

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The synthesis of dinuclear molecular complexes [Eu2(dbm)6(bipyMO)2], 1, [Tb2(dbm)6(bipyMO)2], 2, [Eu2(tta)6(bipyMO)2], 3 [Eu2(hfac)6(bipyMO)3], 4, [Tb2(hfac)6(bipyMO)3], 5 is here reported (bipyMO = 4,4′‐bipyridine N‐oxide, Hdbm = dibenzoylmethane, Htta = thenoyltrifluoroacetone, Hhfac = hexafluoroacetylacetone). The products were obtained in mild conditions and with high yields reacting anhydrous lanthanide β‐diketonates and bipyMO in 1:1 or 1.5 molar ratio in toluene. X‐ray single crystal studies on 2, 3, 4 showed that the heterotopic ligands are hypodentate, bridging the two lanthanide centres exclusively through the oxygen atom. Photoluminescence studies show bright red emissions from europium derivatives with absolute quantum yields up to 44 %.

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“…The selectivity properties of the heterotopic bipyMO ligand in coordinating two different metal ions have been exploited to connect in an ordered chain 4f and 3d ions. In a previous work 26 In the crystal the polymer chains are all parallel running approximately in the [1 10 12] direction. Powder X-ray diffraction patterns carried out on the microcrystalline raw products pointed out that every species (1, 2, 3) was formed by a single crystalline phase, corresponding to the one determined by the single crystal diffraction experiments (Figure 3).…”

Section: Resultsmentioning

confidence: 99%

1D hetero-bimetallic regularly alternated 4f–3d coordination polymers based onN-oxide-4,4′-bipyridine (bipyMO) as a linker: photoluminescence and magnetic properties

et al. 2018

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Heterotopic divergent ligand N-oxide-4,4'-bipyridine (bipyMO) has been herein exploited for the preparation of hetero-bimetallic coordination polymers where Ln(hfac)3 and M(hfac)2 nodes regularly alternate (Hhfac = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione), bipyMO being able to selectively use its two potential coordination sites to discriminate the metal ions. The synthesis of three coordination polymers, [Ln(hfac)3M(hfac)2(bipyMO)2]n (Ln = Eu, M = Zn, 1; Ln = Eu, M = Cu, 2, Ln = Dy, M = Co, 3), was carried out by reacting the appropriate [M(hfac)2(bipyMO)]n and [Ln(hfac)3] precursors in toluene in the presence of a given stoichiometric amount of bipyMO. The products were characterized by elemental analysis, X-ray powder diffraction, and FTIR spectroscopy. Single crystal X-ray diffraction studies carried out on 2 showed that it was formed by chains containing the hexa-coordinated 3d metal (Cu(hfac)2[N]2) and the octa-coordinated lanthanide (Eu(hfac)3[O]2) nodes, where [N] and [O] stand for the donor atom of the bridging divergent ligand. The X-ray powder diffraction patterns of the three compounds and the comparison of their cell constant values allowed establishing that the derivatives were isotypic. Photoluminescence (PL) studies on microcrystalline sample powders evidenced a bright red emission for 1 with an absolute PL quantum yield of 0.24. The sensitized emission of Eu3+ can be excited in a wide wavelength range, from UV to visible, up to ≈450 nm. Conversely, europium emissions are not detectable in 2 due to the presence of Cu(hfac)2(bipyMO) moieties whose strong absorption overlaps Eu3+ transitions. Magnetic measurements conducted on 3 revealed the presence of a weak ferromagnetic interaction below 2.1 K. An ac susceptibility study highlighted a slow relaxation of the magnetization of 3 with an applied static magnetic field of 0.1 T, which could be equally fitted with a Orbach-direct or a Raman-direct mechanism. No relaxation dynamics was detected without the application of a static magnetic field.

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A convenient synthesis of highly luminescent lanthanide 1D-zigzag coordination chains based only on 4,4′-bipyridine as connector

Cited by 19 publications

References 65 publications

1D-Zigzag Eu3+/Tb3+ Coordination Chains as Luminescent Ratiometric Thermometers Endowed with Multicolor Emission

1D-Zigzag Eu3+/Tb3+ Coordination Chains as Luminescent Ratiometric Thermometers Endowed with Multicolor Emission

Homodinuclear Lanthanide Complexes with the Divergent Heterotopic 4,4′‐Bipyridine N‐Oxide (bipyMO) Ligand

1D hetero-bimetallic regularly alternated 4f–3d coordination polymers based onN-oxide-4,4′-bipyridine (bipyMO) as a linker: photoluminescence and magnetic properties

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