Single-crystal-to-single-crystal post-synthetic modifications of three-dimensional LOFs (Ln = Gd, Eu): a way to modulate their luminescence and thermometric properties

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

doi:10.1039/d0dt00449a

Cited by 22 publications

(17 citation statements)

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“…This suggests the existence of not yet considered low-energy levels, able to act as further nonradiative deactivation channels. This situation is often encountered in the presence of low-energy LMCT states ( E LMCT < 25000 cm –1 ). ,,− A commonly accepted method to reveal such transitions in lanthanoid complexes is a comparison of the absorption spectra of Eu 3+ and Gd 3+ compounds. In fact, as the gadolinium first excited state is at ca.…”

Section: Resultsmentioning

confidence: 99%

“…A full description of the employed setup has been previously reported. 63 Mott–Seitz fitting was performed with MATLAB; the curves with R 2 ≥ 0.991 were considered as best-fit curves.…”

Section: Methodsmentioning

confidence: 99%

“…All of the structure solutions were found using the automated direct methods contained in the SHELXS-97 program. 63 Crystal structures of 1 , 3b , and 4 contained, in addition to the dinuclear molecule, also toluene solvate. In the case of 3b , the solvent molecules were so disordered that it was impossible to localize the exact position, and their contribution was subtracted from the electron density map by the SQUEEZE procedure.…”

Section: Methodsmentioning

confidence: 99%

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Composition–Thermometric Properties Correlations in Homodinuclear Eu³⁺ Luminescent Complexes

et al. 2020

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A family of homodinuclear Ln 3+ (Ln 3+ = Gd 3+ , Eu 3+ ) luminescent complexes with the general formula [Ln 2 (β-diketonato) 6 ( N -oxide) y ] has been developed to study the effect of the β-diketonato and N -oxide ligands on their thermometric properties. The investigated complexes are [Ln 2 (tta) 6 (pyrzMO) 2 ] (Ln = Eu ( 1 ·C 7 H 8 ), Gd ( 5 )), [Ln 2 (dbm) 6 (pyrzMO) 2 ] (Ln = Eu ( 2 ), Gd ( 6 )), [Ln 2 (bta) 6 (pyrzMO) 2 ] (Ln = Eu ( 3 ), Gd ( 7 )), [Ln 2 (hfac) 6 (pyrzMO) 3 ] (Ln = Eu ( 4 ), Gd ( 8 )) (pyrzMO = pyrazine N -oxide, Htta = thenoyltrifluoroacetone, Hdbm = dibenzoylmethane, Hbta = benzoyltrifluoroacetone, Hhfac = hexafluoroacetylacetone, C 7 H 8 = toluene), and their 4,4′-bipyridine N -oxide (bipyMO) analogues. Europium complexes emit a bright red light under UV radiation at room temperature, whose intensity displays a strong temperature ( T ) dependence between 223 and 373 K. This remarkable variation is exploited to develop a series of luminescent thermometers by using the integrated intensity of the 5 D 0 → 7 F 2 europium transition as the thermometric parameter (Δ). The effect of different β-diketonato and N -oxide ligands is investigated with particular regard to the shape of thermometer calibration (Δ vs T ) and relative thermal sensitivity curves: i.e.. the change in Δ per degree of temperature variation usually indicated as S r (% K –1 ). The thermometric properties are determined by the presence of two nonradiative deactivation channels, back energy transfer (BEnT) from Eu 3+ to the ligand triplet levels and ligand to metal charge transfer (LMCT). In the complexes bearing tta and dbm ligands, whose triplet energy is ca. 20000 cm –1 , both deactivation channels are active in the same temperature range, and both contribute to determine the thermometric properties. Conversely, with bta and hfac ligands the response of the europium luminescence to temperature variation is ruled by LMCT channels since the high triplet energy (>2...

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Section: Resultsmentioning

confidence: 99%

“…A full description of the employed setup has been previously reported. 63 Mott–Seitz fitting was performed with MATLAB; the curves with R 2 ≥ 0.991 were considered as best-fit curves.…”

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Composition–Thermometric Properties Correlations in Homodinuclear Eu³⁺ Luminescent Complexes

et al. 2020

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“…The temperature resolution of our thermometers, i.e., the smallest detectable temperature variation (δT), was determined by the heating/freezing cycles, according to literature [ 2 , 3 , 18 ], using the following equation:

where δΔ is the Δ uncertainty at a given temperature [ 3 , 6 ] determined by calculating the standard deviation of three heating/freezing cycles. All the samples showed comparable resolution in the order of 0.01 K (average value over the thermometer operational range), in line with literature values for Ln-based luminescence thermometers [ 2 , 3 ].…”

Section: Resultsmentioning

confidence: 99%

“…Lanthanide Metal–Organic Frameworks (MOFs) and Coordination Polymers (CPs) immediately appeared to be excellent platforms for the development of ratiometric thermometers [ 3 , 11 , 15 , 17 , 18 ]. Indeed, the possibility to introduce different metal ions simultaneously in MOFs and CPs, without altering their structure, marked them as two of the most promising materials for the development of luminescent thermometers.…”

Section: Introductionmentioning

confidence: 99%

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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Recent Progress of Multiferroicity and Magnetoelectric Effects in ABX₃‐Type Perovskite Metal–Organic Frameworks

Wang

2023

Adv Materials Inter

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Multiferroics have been investigated extensively in the last decades due to their wide range of applications in high‐density multistate storage, spintronics, and novel multifunctional magnetic–electric devices. One peculiar subgroup of multiferroic materials comprises 3D perovskite metal–organic frameworks (MOFs) with the general formula ABX3 (A = monovalent organic cation (such as an alkali metal or protonated amine), B = divalent metal cation, X = organic anion), for their coexistence of multiple orders (electric, magnetic, and elastic, et al.). The purpose of this review is to give a representative overview of the recent progress in the field of ABX3‐type multiferroic MOFs, containing 3d magnetic metal ions at B‐site. First, the perovskite multiferroic MOFs in which X‐site is occupied by formate, is examined and summarized. In particular, magnetoelectric coupling effects, such as electric‐field tuning of magnetic properties and magnetic field control of electric polarization, and pressure control of structural/magnetic/electric properties, are described and discussed. Then, it is focused on the structural phase transitions and ferroic orders by analyzing several representative multiferroic MOFs compounds with none‐formate. To motivate the researchers in this area, some promising topics that have not yet been fully explored in perovskite multiferroic MOFs are finally proposed.

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Single-crystal-to-single-crystal post-synthetic modifications of three-dimensional LOFs (Ln = Gd, Eu): a way to modulate their luminescence and thermometric properties

Abstract: Single-crystal-to-single-crystal post-synthetic modifications of {[Ln2(H2L)3(DMF)4]·2DMF}n LOFs (Ln = Gd, Eu) to modulate their luminescence and thermometric properties.

Cited by 22 publications

References 49 publications

Composition–Thermometric Properties Correlations in Homodinuclear Eu³⁺ Luminescent Complexes

Composition–Thermometric Properties Correlations in Homodinuclear Eu³⁺ Luminescent Complexes

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

Recent Progress of Multiferroicity and Magnetoelectric Effects in ABX₃‐Type Perovskite Metal–Organic Frameworks

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Single-crystal-to-single-crystal post-synthetic modifications of three-dimensional LOFs (Ln = Gd, Eu): a way to modulate their luminescence and thermometric properties

Abstract: Single-crystal-to-single-crystal post-synthetic modifications of {[Ln2(H2L)3(DMF)4]·2DMF}n LOFs (Ln = Gd, Eu) to modulate their luminescence and thermometric properties.

Cited by 22 publications

References 49 publications

Composition–Thermometric Properties Correlations in Homodinuclear Eu3+ Luminescent Complexes

Composition–Thermometric Properties Correlations in Homodinuclear Eu3+ Luminescent Complexes

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

Recent Progress of Multiferroicity and Magnetoelectric Effects in ABX3‐Type Perovskite Metal–Organic Frameworks

Contact Info

Product

Resources

About

Composition–Thermometric Properties Correlations in Homodinuclear Eu³⁺ Luminescent Complexes

Composition–Thermometric Properties Correlations in Homodinuclear Eu³⁺ Luminescent Complexes

Recent Progress of Multiferroicity and Magnetoelectric Effects in ABX₃‐Type Perovskite Metal–Organic Frameworks