Recent advances on high-nuclear polyoxometalate clusters

Liu, Jian‐Cai; Zhao, Junwei; Streb, Carsten; Song, Yufei

doi:10.1016/j.ccr.2022.214734

Cited by 81 publications

(55 citation statements)

References 263 publications

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“…The abundant oxygen atoms on the surface of the POMs are coordination sites for lanthanide ions, especially the lacunary POMs has more well-defined coordination sites and stronger nucleophilic ability. Thus, the lacunary POMs can be used as multi-dentate inorganic ligands to stabilize the LnOCs, forming cluster-of-cluster aggregates [24][25][26][27][28][29][38][39][40][41]. The POMs themself are particularly suitable as proton-conducting materials due to the oxygen-rich sites for proton transfer jumps, the discrete mobile ionic constituents, and the "pseudo-liquid phase" behavior [27][28][29].…”

Section: Instructionmentioning

confidence: 99%

“…Up to now, large numbers of POMs-based LnOCs with a rich variety of structures and interesting properties have been reported. However, compared with the POMs-based 3d-transition metal clusters and organic ligand-based LnOCs, the development of POMs-based LnOCs is still lagging behind, and the synthesis of high-nuclearity LnOCs still lacks a proven method [18][19][20][21][22][23][38][39][40][41]. In this review, we summarize the development of the most widely studied LnOCs related to polyoxotungstates, including structural classification, synthesis strategies, and some properties, and briefly discuss our personal views on their future research directions.…”

Section: Instructionmentioning

confidence: 99%

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Recent advances in polyoxometalate-based lanthanide–oxo clusters

Liu

et al. 2023

Polyoxometalates

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Polyoxometalates (POMs)-based lanthanide-oxo clusters (LnOCs) are a class of polynuclear lanthanide-oxygen complexes formed by polyoxometalates stabilization through oxygen bridge linkage, in which the POMs can be viewed as multi-dentate inorganic ligands. The POMs-based LnOCs have received a lot of attention because of their interesting structures and potential applications. In this paper, we summarize the classification, synthesis strategies, and properties of POMs-based LnOCs. Herein, the POMs-based LnOCs are classified into three main categories according to their metal core element types and quantities: pure 4f clusters, 5d-4f clusters, and 3d-4f clusters. Their synthetic strategies are grouped into four categories based on the source of the POMs involved in the structural assembly: lacunary POMs ligand-directed method, in-situ transformation of lacunary POMs ligand-directed method, in-situ generation of lacunary POMs ligand-directed method, and mixing multiple synthesis strategies. The single-molecule magnets and proton conductivity properties of POMs-based LnOCs are summarized.

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Section: Instructionmentioning

confidence: 99%

Section: Instructionmentioning

confidence: 99%

Recent advances in polyoxometalate-based lanthanide–oxo clusters

Liu

et al. 2023

Polyoxometalates

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“…Therefore, POMOF materials could be regarded as one of the ideal candidates for efficient heterogeneous catalysts. Several relative POMOF materials with diverse constitutions and configurations have been reported − and further explored their catalytic abilities mainly focused on photocatalytic or electrocatalytic hydrogen evolution, CO 2 reduction, , oxidation of alkylbenzenes to aldehydes, , olefin epoxidation, or oxidation of silanes. , The catalytic synthesis of quinazolinones and their derivatives based on POMOF catalysts still remains large to explore.…”

Section: Introductionmentioning

confidence: 99%

Structural Regulation of Two Polyoxometalate-Based Metal–Organic Frameworks for the Heterogeneous Catalysis of Quinazolinones

et al. 2023

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Two dimeric {ε-Zn 4 PMo 12 }-based metal−organic frameworks (MOFs), [ε-PMo 8 V Mo 4 VI O 34 (OH) 6 Zn 4 ][LO] (SDUT-21, LO = [5-((4′-carboxybenzyl)oxy)isophthalic acid]) and [TBA] 3 [ε-PMo 8 V Mo 4 VI O 37 (OH) 3 Zn 4 ][LN] (SDUT-22, TBA + = tetrabutylammonium ion, LN = [5-((4-carboxybenzyl)imino)isophthalic acid]), combining the advantages of polyoxometalates (POMs) and MOFs, were synthesized by the one-pot assembly strategy. The dimeric {ε-Zn 4 PMo 12 } units act as nodes that are linked by the flexible ligands and extended into two-or threedimensional frameworks. The cyclic voltammetry and proton conductivity measurements of SDUT-21 and SDUT-22 were performed and indicated the high electron and proton transfer abilities. These materials also e xhibited the catalytic performance for the synthesis of quinazolinones in the heterogeneous state, and the different binding capacities toward the substrates caused the catalytic activity of SDUT-21 to be higher than that of SDUT-22 under the same conditions. In addition, the used catalysts could be readily recovered for five successive cycles and maintained high catalytic efficiency.

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“…In particular, lacunary POMs offer flexibility of coordination modes and highly reactive vacant sites toward metal ions. Currently, there is increasing interest in the design and synthesis of POMs featuring high-nuclearity transition metal (TM)/lanthanoid (Ln) centers due to their unique catalytic, electronic, and magnetic properties as well as structural aesthetic appreciation . These molecular POMs can be regarded as excellent nanosized inorganic building blocks for the construction of purely inorganic or hybrid organic–inorganic 1D chains, 2D sheets, or 3D network solids .…”

Section: Introductionmentioning

confidence: 99%

Heteroatom-Modulated Assembly of Hexalanthanoid-Containing Polyoxometalate-Based Coordination Networks

et al. 2023

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Two series of lanthanoid (Ln)-containing polyoxometalates (POMs) {[Ln6(ampH)4(H2O)24–n (ampH2) n (PW11O39)2]·21H2O (Ln = Tb, n = 0 (1), Ln = Er, n = 1 (2)) and K2[Ln6(ampH)4(H2O)22(SiW11O39)2]·23H2O (Ln = Tb (3), Er (4)) (ampH2 = (aminomethyl) phosphonic acid)} have been synthesized with tri-lacunary Keggin-type POMs containing different types of heteroatoms. Compounds 1 and 2 display neutral organic–inorganic hybrid POM molecules containing {Ln6(ampH)4} ({Ln6}) cores sandwiched by two {PW11O39} units. By changing the heteroatoms from PV to SiIV, the extended 2D networks of 3 and 4 were successfully isolated where the adjacent {Ln6} clusters were connected by {SiW11O39} moieties. Luminescence performances and magnetic properties of 1–4 have been systematically surveyed. The solid-state fluorescence spectra of 1–4 display characteristic emissions of Ln components resulting from the 4f–4f transitions, and energy transfer from the POM segments to Ln3+ centers in 1 and 3 has been observed based on the lifetime decay behaviors. Furthermore, all compounds can be utilized as electrocatalysts toward reduction of nitrite with high stability.

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Recent advances on high-nuclear polyoxometalate clusters

Cited by 81 publications

References 263 publications

Recent advances in polyoxometalate-based lanthanide–oxo clusters

Recent advances in polyoxometalate-based lanthanide–oxo clusters

Structural Regulation of Two Polyoxometalate-Based Metal–Organic Frameworks for the Heterogeneous Catalysis of Quinazolinones

Heteroatom-Modulated Assembly of Hexalanthanoid-Containing Polyoxometalate-Based Coordination Networks

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