Hetero-hexalanthanide Complexes: A New Synthetic Strategy for Molecular Thermometric Probes

Yao, Haiyun; Calvez, Guillaume; Daiguebonne, Carole; Bernot, Kévin; Suffren, Yan; Guillou, Olivier

doi:10.1021/acs.inorgchem.9b02668

Cited by 14 publications

(13 citation statements)

References 83 publications

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“…[54][55][56][57] There are, however,s ome remarkable exampleso fh omo-or heterometallic Ln-to-Ln ET studies taking place within discretem olecules. [35,48,[58][59][60][61][62][63][64][65][66] Most of them are conducted in solution,w ith polydentate ligandsi nt he presence of two different lanthanide ions. [67][68][69] In many of these systems, there is little-to-no control over the location of each Ln III in the molecular scaffold, which is mainly dictated by statisticals peciation.…”

Section: Introductionmentioning

confidence: 99%

Accessing Lanthanide‐to‐Lanthanide Energy Transfer in a Family of Site‐Resolved [Ln^IIILn^III′] Heterodimetallic Complexes

Galán

Aguilà

Guyot

et al. 2021

Chemistry A European J

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The ligand H 3 L( 6-[3-oxo-3-(2-hydroxyphenyl)propionyl]pyridine-2-carboxylic acid), which exhibits two different coordination pockets, has been exploitedt oe ngender and study energy transfer (ET) in two dinuclear [Ln III Ln III ']a nalogueso fi nterest, [EuYb] and [NdYb]. Their structurala nd physical properties have been compared with newly synthesiseda nalogues featuring no possible ET ([EuLu],[ NdLu], and [GdYb]) and with the corresponding homometallic [EuEu] and[ NdNd] analogues,w hich have been previously reported. Photophysicald ata suggest that ET between Eu III and Yb III does not occur to as ignificant extent, whereas emission from Yb III originates from sensitisation of the ligand. In contrast, energy migration seems to be occurring betweent he two Nd III centres in [NdNd],a sw ell as in [NdYb],inwhich Yb III luminescenceisthus, in part, sensitised by ET from Nd. This study shows the versatility of this molecular platform to further the investigation of lanthanide-tolanthanide ET phenomena in defined molecular systems.

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Section: Introductionmentioning

confidence: 99%

Accessing Lanthanide‐to‐Lanthanide Energy Transfer in a Family of Site‐Resolved [Ln^IIILn^III′] Heterodimetallic Complexes

Galán

Aguilà

Guyot

et al. 2021

Chemistry A European J

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“…Polynuclear Ln 3+ clusters attract increasing attention, as a result of their intriguing geometrical features and interesting properties related to magnetic, quantum computing and luminescent applications. The reported Ln 3+ clusters mainly include trinuclear (Ln 3 , Ln = Gd, Tb, Dy, Ho), [16,17] tetranuclear (Ln 4 , Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb), [18][19][20][21][22][23][24][25][26][27] pentanuclear (Ln 5 , Ln = Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb), [25] hexanuclear (Ln 6 , Ln = Pr, Ce, Eu, Gd, Tb, Dy, Er and Y), [27][28][29][30] octagon (Ln 8 , Ln = Gd, Tb, Dy, Ho), [31] nine-nuclear (Ln 9 , Ln = Nd, Sm, Eu, Gd, Tb, Dy, Ho), [32][33][34] eleven-nuclear (Ln 11 , Ln = Gd, Tb, Dy), [35] dodecanuclear (Ln 12 , Ln = Eu, Gd, Tb, Dy), [32,[36][37][38] hexadecanuclear (Ln 16 , Ln = Gd, Dy) clusters. [39] The number of Ln nuclei in Ln 3+ clusters was often controlled by the preferred coordination geometry of ligands [32] and the reaction environments.…”

Section: Cluster Chemistry Of Group 3 and 4 Metalsmentioning

confidence: 99%

“…[ 109 ] Guillou and co‐workers reported that solvothermal or microwave‐assisted reactions between RE 6 clusters (RE = Eu‐Dy, Y) and m‐halogeno‐benzoic acids can lead to MOFs with formula [RE 6 (μ 3 ‐OH) 2 (H 2 O) 2 (NO 3 ) 2 (3‐L) 14 ] (L = 3‐chloro‐, 3‐bromo‐, and 3‐iodo‐benzoate). [ 28 ] RE cations located at each vertex of quasi‐planar hexagon formed by two almost‐perfect equilateral triangles. Detailed study of luminescent properties revealed that these MOFs own strong intermetallic energy transfers, placing them promising candidates for thermometric probes in solid or solution state.…”

Section: Mofs Based On Y and Lns (Group 3 Metals)mentioning

confidence: 99%

Metal–Organic Frameworks Based on Group 3 and 4 Metals

et al. 2020

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Metal-organic frameworks (MOFs), a class of porous crystalline framework materials, are linked by strong bonds between inorganic and organic building blocks. [1-3] In the past two decades, MOFs have rapidly grown as a star material due to their exceptional performance in areas such as storage, separation and catalysis. [4] The outstanding performance of MOFs in applications benefits from their intrinsically porous structures and highly tunable pore environment. [5-7] The creation and modification of pore space with optimized size, functionality and diversity can be precisely tuned at the molecular level by rationally designing building blocks and synthetic procedures. [8,9] The diversity of MOFs can be enriched by expanding the library of organic linkers with varying lengths, geometries, and functional groups. [10] Additionally, very diverse metal cations are applied to MOF synthesis, ranging from monovalent (Ag + , Cu + , etc.), divalent (Mg 2+ , Fe 2+ , Co 2+ , Ni 2+ , etc.), trivalent (Al 3+ , Sc 3+ , V 3+ , Cr 3+ , etc.), to tetravalent (Ti 4+ , Zr 4+ , Hf 4+ , etc.) cations. [11] In this review, we mainly focus on MOFs with group 3 and 4 metals, including Y, lanthanides (Ln, from La to Lu), actinides (An, from Ac to Lr), Ti, and Zr (Figure 1). Group 3 metal cations are generally found in the oxidation state of +3 in the MOF structures, while group 4 metal cations mainly exist in the oxidation state of +4, leading to the formation of much stronger coordination bonds with carboxylates. [12] Therefore, group 4 metal-based MOFs (M IV-MOFs) generally have enhanced stability compared with MOFs constructed from metals of group 3 and other groups. This series of MOFs stands out because the involved metals can generally coordinate with carboxylates to form frameworks with strong coordination bonds, according to the Pearson's hard/soft acid/base principle, where group 3 and 4 metal cations are regarded as hard acids while carboxylate ligands are hard bases. [11] One remarkable feature of MOFs with group 3 and 4 metals is that they generally can form phases containing M 6 O 8 (M = Y, Ln, An, Zr and Hf) clusters, regardless of their atomic numbers, charges and radius. This series of M 6-based MOFs is best represented by UiO series such as UiO-66 with fcu topology. [13] Under different synthetic conditions, UiO-66(M, M = An, Zr and Hf) constructed from [M 6 (μ 3-O) 4 (μ 3-OH) 4 ] clusters and linear carboxylates can be obtained, while UiO-66(M, M = Y, Ln) is assembled from Metal-organic frameworks (MOFs) based on group 3 and 4 metals are considered as the most promising MOFs for varying practical applications including water adsorption, carbon conversion, and biomedical applications. The relatively strong coordination bonds and versatile coordination modes within these MOFs endow the framework with high chemical stability, diverse structures and topologies, and interesting properties and functions. Herein, the significant progress made on this series of MOFs since 2018 is summarized and an update on the current status an...

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“…Recently, Calvez and coworkers reported a series of hexalanthanide clusters with m-halogenobenzoic acid ligands as solid molecular thermometric probes. 126 Shown in Fig. 25 is the structure of a hexa-Dy cluster 29, [Dy 6 (3-bb) 14 ] (3-bb = m-bromo-benzoic acid).…”

Section: Organic-inorganic Hybrid Clustersmentioning

confidence: 99%

Thermo-responsive light-emitting metal complexes and related materials

Gong

et al. 2020

Inorg. Chem. Front.

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Hetero-hexalanthanide Complexes: A New Synthetic Strategy for Molecular Thermometric Probes

Cited by 14 publications

References 83 publications

Accessing Lanthanide‐to‐Lanthanide Energy Transfer in a Family of Site‐Resolved [Ln^IIILn^III′] Heterodimetallic Complexes

Accessing Lanthanide‐to‐Lanthanide Energy Transfer in a Family of Site‐Resolved [Ln^IIILn^III′] Heterodimetallic Complexes

Metal–Organic Frameworks Based on Group 3 and 4 Metals

Thermo-responsive light-emitting metal complexes and related materials

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Hetero-hexalanthanide Complexes: A New Synthetic Strategy for Molecular Thermometric Probes

Cited by 14 publications

References 83 publications

Accessing Lanthanide‐to‐Lanthanide Energy Transfer in a Family of Site‐Resolved [LnIIILnIII′] Heterodimetallic Complexes

Accessing Lanthanide‐to‐Lanthanide Energy Transfer in a Family of Site‐Resolved [LnIIILnIII′] Heterodimetallic Complexes

Metal–Organic Frameworks Based on Group 3 and 4 Metals

Thermo-responsive light-emitting metal complexes and related materials

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Product

Resources

About

Accessing Lanthanide‐to‐Lanthanide Energy Transfer in a Family of Site‐Resolved [Ln^IIILn^III′] Heterodimetallic Complexes

Accessing Lanthanide‐to‐Lanthanide Energy Transfer in a Family of Site‐Resolved [Ln^IIILn^III′] Heterodimetallic Complexes