Home Polyoxometalates Article
PDF (48.3 MB)
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript
Show Outline
Figures (24)

Show 15 more figures Hide 15 figures
Tables (5)
Table 1
Table 2
Table 3
Table 4
Table 5
Review Article | Open Access

Recent advances in polyoxometalate-based lanthanide–oxo clusters

Shu-Rong Li, Wei-Dong Liu, La-Sheng Long, Lan-Sun Zheng, Xiang-Jian Kong ()
Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
Show Author Information

Graphical Abstract

View original image Download original image

Abstract

Polyoxometalate (POM)-based lanthanide-oxo clusters (LnOCs) are a class of polynuclear lanthanide–oxygen complexes formed by polyoxometalate stabilization through oxygen bridges in which POMs can be viewed as multidentate inorganic ligands. POM-based LnOCs have received interest owing to their interesting structures and potential applications. In this paper, we summarize the classification, synthesis strategies, and properties of POM-based LnOCs. POM-based LnOCs are classified into three main categories according to their metal core element type and quantity: pure 4f clusters, 5d–4f clusters, and 3d–4f clusters. Their synthetic strategies are divided into four categories based on the source of the POM involved in the structural assembly: the lacunary POMs ligand-directed method, the in-situ transformation of lacunary POMs ligand-directed method, the in-situ generation of lacunary POMs ligand-directed method, and mixed synthesis strategies. In addition, the single-molecule magnets of POM-based LnOCs and their proton conduction properties are summarized.

Keywords

polyoxometalateslanthanideclusterssynthetic strategyapplications

References

[1]

Guo, F. S.; Day, B. M.; Chen, Y. C.; Tong, M. L.; Mansikkamäki, A.; Layfield, R. A. Magnetic hysteresis up to 80 kelvin in a dysprosium metallocene single-molecule magnet. Science 2018, 362, 1400–1403.

Crossref Google Scholar
[2]

Fu, X.; Fu, S.; Lu, Q.; Zhang, J.; Wan, P. P.; Liu, J. L.; Zhang, Y.; Chen, C. H.; Li, W.; Wang, H. D. et al. Excitation energy mediated cross-relaxation for tunable upconversion luminescence from a single lanthanide ion. Nat. Commun. 2022, 13, 4741.

Crossref Google Scholar
[3]

Xu, Q. F.; Liu, B. L.; Ye, M. Y.; Zhuang, G. L.; Long, L. S.; Zheng, L. S. Gd(OH)F2: A promising cryogenic magnetic refrigerant. J. Am. Chem. Soc. 2022, 144, 13787–13793.

Crossref Google Scholar
[4]

Schroll, C. A.; Chatterjee, S.; Levitskaia, T. G.; Heineman, W. R.; Bryan, S. A. Electrochemistry and Spectroelectrochemistry of Europium (III) Chloride in 3LiCl-2KCl from 643 to 1123 K. Anal. Chem. 2013, 85, 9924–9931.

Crossref Google Scholar
[5]

Li, X. Z.; Tian, C. B.; Sun, Q. F. Coordination-directed self-assembly of functional polynuclear lanthanide supramolecular architectures. Chem. Rev. 2022, 122, 6374–6458.

Crossref Google Scholar
[6]

Sahoo, S.; Mondal, S.; Sarma, D. Luminescent lanthanide metal organic frameworks (LnMOFs): A versatile platform towards organomolecule sensing. Coord. Chem. Rev. 2022, 470, 214707.

Crossref Google Scholar
[7]

Chen, R.; Chen, C. L.; Du, M. H.; Wang, X.; Wang, C.; Long, L. S.; Kong, X. J.; Zheng, L. S. Soluble lanthanide-transition-metal clusters Ln36Co12 as effective molecular electrocatalysts for water oxidation. Chem. Commun. (Camb.) 2021, 57, 3611–3614.

Crossref Google Scholar
[8]

Du, M. H.; Chen, L. Q.; Jiang, L. P.; Liu, W. D.; Long, L. S.; Zheng, L. S.; Kong, X. J. Counterintuitive lanthanide hydrolysis-induced assembly mechanism. J. Am. Chem. Soc. 2022, 144, 5653–5660.

Crossref Google Scholar
[9]

Du, M. H.; Wang, D. H.; Wu, L. W.; Jiang, L. P.; Li, J. P.; Long, L. S.; Zheng, L. S.; Kong, X. J. Hierarchical assembly of coordination macromolecules with atypical geometries: Gd44Co28 crown and Gd95Co60 cage. Angew. Chem., Int. Ed. 2022, 61, e202200537.

Crossref Google Scholar
[10]

Liu, W. D.; Li, G. J.; Xu, H.; Du, M. H.; Long, L. S.; Zheng, L. S.; Kong, X. J. Photoluminescence of lanthanide-titanium-oxo clusters Eu9Ti2 and Tb9Ti2 based on a β-diketone ligand. Inorg. Chem. 2022, 61, 9849–9854.

Crossref Google Scholar
[11]

Wang, X.; Wang, S. Q.; Chen, J. N.; Jia, J. H.; Wang, C.; Paillot, K.; Breslavetz, I.; Long, L. S.; Zheng, L. S.; Rikken, G. L. J. A. et al. Magnetic 3d-4f chiral clusters showing multimetal site magneto-chiral dichroism. J. Am. Chem. Soc. 2022, 144, 8837–8847.

Crossref Google Scholar
[12]

Weng, Z. Z.; Xie, J.; Huang, K. X.; Li, J. P.; Long, L. S.; Kong, X. J.; Zheng, L. S. Asymmetric cyanosilylation of aldehydes by a lewis acid/base synergistic catalyst of chiral metal clusters. Inorg. Chem. 2022, 61, 4121–4129.

Crossref Google Scholar
[13]

Chen, R.; Hong, Z. F.; Zhao, Y. R.; Zheng, H.; Li, G. J.; Zhang, Q. C.; Kong, X. J.; Long, L. S.; Zheng, L. S. Ligand-dependent luminescence properties of lanthanide-titanium oxo clusters. Inorg. Chem. 2019, 58, 15008–15012.

Crossref Google Scholar
[14]

Chen, R.; Yan, Z. H.; Kong, X. J.; Long, L. S.; Zheng, L. S. Integration of lanthanide-transition-metal clusters onto CdS surfaces for photocatalytic hydrogen evolution. Angew. Chem., Int. Ed. 2018, 57, 16796–16800.

Crossref Google Scholar
[15]

Chen, R.; Zhuang, G. L.; Wang, Z. Y.; Gao, Y. J.; Li, Z.; Wang, C.; Zhou, Y.; Du, M. H.; Zeng, S. Y.; Long, L. S. et al. Integration of bio-inspired lanthanide-transition metal cluster and P-doped carbon nitride for efficient photocatalytic overall water splitting. Natl. Sci. Rev. 2021, 8, nwaa234.

Crossref Google Scholar
[16]

Jin, P. B.; Yu, K. X.; Luo, Q. C.; Liu, Y. Y.; Zhai, Y. Q.; Zheng, Y. Z. Tetraanionic arachno-carboranyl ligand imparts strong axiality to terbium(III) single-molecule magnets. Angew. Chem., Int. Ed. 2022, 61, e202203285.

Crossref Google Scholar
[17]

Zhang, H. L.; Zhai, Y. Q.; Nojiri, H.; Schröder, C.; Hsu, H. K.; Chan, Y. T.; Fu, Z. D.; Zheng, Y. Z. {ScnGdn} heterometallic rings: Tunable ring topology for spin-wave excitations. J. Am. Chem. Soc. 2022, 144, 15193–15202.

Crossref Google Scholar
[18]

Chen, S. S.; Su, H. F.; Long, L. S.; Zheng, L. S.; Kong, X. J. Hydrolysis-promoted building block assembly: Structure transformation from Y12 wheel and Y34 ship to Y60 cage. Inorg. Chem. 2021, 60, 16922–16926.

Crossref Google Scholar
[19]

Du, M. H.; Xu, S. H.; Li, G. J.; Xu, H.; Lin, Y.; Liu, W. D.; Long, L. S.; Zheng, L. S.; Kong, X. J. Modification of multi-component building blocks for assembling giant chiral lanthanide-titanium molecular rings. Angew. Chem., Int. Ed. 2022, 61, e202116296.

Crossref Google Scholar
[20]

Huang, W. M.; Chen, W. M.; Bai, Q. X.; Zhang, Z.; Feng, M.; Zheng, Z. P. Anion-guided stepwise assembly of high-nuclearity lanthanide hydroxide clusters. Angew. Chem., Int. Ed. 2022, 61, e202205385.

Crossref Google Scholar
[21]

Pan, Z. H.; Weng, Z. Z.; Kong, X. J.; Long, L. S.; Zheng, L. S. Lanthanide-containing clusters for catalytic water splitting and CO2 conversion. Coord. Chem. Rev. 2022, 457, 214419.

Crossref Google Scholar
[22]

Zheng, X. Y.; Kong, X. J.; Zheng, Z. P.; Long, L. S.; Zheng, L. S. High-nuclearity lanthanide-containing clusters as potential molecular magnetic coolers. Acc. Chem. Res. 2018, 51, 517–525.

Crossref Google Scholar
[23]

Zheng, X. Y.; Xie, J.; Kong, X. J.; Long, L. S.; Zheng, L. S. Recent advances in the assembly of high-nuclearity lanthanide clusters. Coord. Chem. Rev. 2019, 378, 222–236.

Crossref Google Scholar
[24]

Das, V.; Kaushik, R.; Hussain, F. Heterometallic 3d-4f polyoxometalates: An emerging field with structural diversity to multiple applications. Coord. Chem. Rev. 2020, 413, 213271.

Crossref Google Scholar
[25]

Fang, X. K.; Kögerler, P.; Speldrich, M.; Schilder, H.; Luban, M. A polyoxometalate-based single-molecule magnet with an S = 21/2 ground state. Chem. Commun. (Camb.) 2012, 48, 1218–1220.

Crossref Google Scholar
[26]

Ma, X.; Yang, W.; Chen, L. J.; Zhao, J. W. Significant developments in rare-earth-containing polyoxometalate chemistry: Synthetic strategies, structural diversities and correlative properties. CrystEngComm 2015, 17, 8175–8197.

Crossref Google Scholar
[27]

Meng, X.; Wang, H. N.; Song, S. Y.; Zhang, H. J. Proton-conducting crystalline porous materials. Chem. Soc. Rev. 2017, 46, 464–480.

Crossref Google Scholar
[28]

Ogiwara, N.; Iwano, T.; Ito, T.; Uchida, S. Proton conduction in ionic crystals based on polyoxometalates. Coord. Chem. Rev. 2022, 462, 214524.

Crossref Google Scholar
[29]

Yang, P.; Alsufyani, M.; Emwas, A. H.; Chen, C. Q.; Khashab, N. M. Lewis acid guests in a {P8W48} archetypal polyoxotungstate host: Enhanced proton conductivity via metal-oxo cluster within cluster assemblies. Angew. Chem., Int. Ed. 2018, 57, 13046–13051.

Crossref Google Scholar
[30]

Boskovic, C. Rare earth polyoxometalates. Acc. Chem. Res. 2017, 50, 2205–2214.

Crossref Google Scholar
[31]

Wang, Z. M.; Xin, X.; Zhang, M.; Li, Z.; Lv, H. J.; Yang, G. Y. Recent advances of mixed-transition-metal-substituted polyoxometalates. Sci. China Chem. 2022, 65, 1515–1525.

Crossref Google Scholar
[32]

Liu, J. C.; Zhao, J. W.; Streb, C.; Song, Y. F. Recent advances on high-nuclear polyoxometalate clusters. Coord. Chem. Rev. 2022, 471, 214734.

Crossref Google Scholar
[33]

Zhao, J. W.; Li, Y. Z.; Chen, L. J.; Yang, G. Y. Research progress on polyoxometalate-based transition-metal-rare-earth heterometallic derived materials: Synthetic strategies, structural overview and functional applications. Chem. Commun. (Camb.) 2016, 52, 4418–4445.

Crossref Google Scholar
[34]

Bijelic, A.; Aureliano, M.; Rompel, A. Polyoxometalates as potential next-generation metallodrugs in the combat against cancer. Angew. Chem., Int. Ed. 2019, 58, 2980–2999.

Crossref Google Scholar
[35]

Chen, X. L.; Zhou, Y.; Roy, V. A. L.; Han, S. T. Evolutionary metal oxide clusters for novel applications: Toward high-density data storage in nonvolatile memories. Adv. Mater. 2018, 30, 1703950.

Crossref Google Scholar
[36]

Liu, J. X.; Zhang, X. B.; Li, Y. L.; Huang, S. L.; Yang, G. Y. Polyoxometalate functionalized architectures. Coord. Chem. Rev. 2020, 414, 213260.

Crossref Google Scholar
[37]

Sun, M.; Zhang, J. Z.; Putaj, P.; Caps, V.; Lefebvre, F.; Pelletier, J.; Basset, J. M. Catalytic oxidation of light alkanes (C1-C4) by heteropoly compounds. Chem. Rev. 2014, 114, 981–1019.

Crossref Google Scholar
[38]

Yang, L.; Lei, J.; Fan, J. M.; Yuan, R. M.; Zheng, M. S.; Chen, J. J.; Dong, Q. F. The intrinsic charge carrier behaviors and applications of polyoxometalate clusters based materials. Adv. Mater. 2021, 33, 2005019.

Crossref Google Scholar
[39]

Zhang, M.; Li, H. J.; Zhang, J. H.; Lv, H. J.; Yang, G. Y. Research advances of light-driven hydrogen evolution using polyoxometalate-based catalysts. Chin. J. Catal. 2021, 42, 855–871.

Crossref Google Scholar
[40]

Zhao, H. Y.; Li, Y. Z.; Zhao, J. W.; Wang, L.; Yang, G. Y. State-of-the-art advances in the structural diversities and catalytic applications of polyoxoniobate-based materials. Coord. Chem. Rev. 2021, 443, 213966.

Crossref Google Scholar
[41]

Peacock, R. D.; Weakley, T. J. R. Heteropolytungstate complexes of the lanthanide elements. Part I. Preparation and reactions. J. Chem. Soc. A 1971, 1836–1839

Crossref Google Scholar
[42]

Peacock, R. D.; Weakley, T. J. R. Heteropolytungstate complexes of the lanthanide elements. Part Ⅱ. Electronic spectra:A metal-ligand charge-transfer transition of cerium (Ⅲ). J. Chem. Soc. A 1971, 1937–1940

Crossref Google Scholar
[43]

Lin, Y. D.; Ge, R.; Tian, C. B.; Sun, C.; Sun, Y. Q.; Zeng, Q. X.; Li, X. X.; Zheng, S. T. 3d-4f Heterometallic cluster incorporated polyoxoniobates with magnetic properties. Chem. Commun. (Camb.) 2021, 57, 8624–8627.

Crossref Google Scholar
[44]

Ribó, E. G.; Bell, N. L.; Long, D. L.; Cronin, L. Engineering highly reduced molybdenum polyoxometalates via the incorporation of d and f block metal ions. Angew. Chem., Int. Ed. 2022, 61, e202201672.

Crossref Google Scholar
[45]

Jin, L.; Li, X. X.; Qi, Y. J.; Niu, P. P.; Zheng, S. T. Giant hollow heterometallic polyoxoniobates with sodalite-type lanthanide-tungsten-oxide cages: Discrete nanoclusters and extended frameworks. Angew. Chem., Int. Ed. 2016, 55, 13793–13797.

Crossref Google Scholar
[46]

Sadakane, M.; Dickman, M. H.; Pope, M. T. Controlled assembly of polyoxometalate chains from lacunary building blocks and lanthanide-cation linkers. Angew. Chem., Int. Ed. 2000, 39, 2914–2916.

Crossref Google Scholar
[47]

Ibrahim, M.; Mbomekallé, I. M.; De Oliveira, P.; Baksi, A.; Carter, A. B.; Peng, Y.; Bergfeldt, T.; Malik, S.; Anson, C. E. Syntheses, crystal structure, electrocatalytic, and magnetic properties of the monolanthanide-containing germanotungstates [Ln(H2O)nGe W11O39]5− (Ln = Dy, Er, n = 4, 3). ACS Omega 2019, 4, 21873–21882.

Crossref Google Scholar
[48]

Cañón-Mancisidor, W.; Zapata-Lizama, M.; Hermosilla-Ibáñez, P.; Cruz, C.; Venegas-Yazigi, D.; Espallargas, G. M. Hybrid organic-inorganic mononuclear lanthanoid single ion magnets. Chem. Commun. (Camb.) 2019, 55, 14992–14995.

Crossref Google Scholar
[49]

Jing, J. X.; Shi, N.; Sun, Y. Q.; Li, X. X.; Zheng, S. T. An inorganic-organic hybrid polyoxotungstogermanate based on [Ln(α-GeW11O39)2] dimer and dimethylammonium: Synthesis, crystal structure and photoluminescence property. J. Mol. Struct. 2022, 1250, 131686.

Crossref Google Scholar
[50]

Mougharbel, A. S.; Bhattacharya, S.; Bassil, B. S.; Rubab, A.; Van Leusen, J.; Kögerler, P.; Wojciechowski, J.; Kortz, U. Lanthanide-containing 22-tungsto-2-germanates [Ln(GeW11O39)2]13−: Synthesis, structure, and magnetic properties. Inorg. Chem. 2020, 59, 4340–4348.

Crossref Google Scholar
[51]

Wan, R.; Ma, P. T.; Han, M. D.; Zhang, D. D.; Zhang, C.; Niu, J. Y.; Wang, J. P. Discovery and isolation of the trans-isomers of two 1:2-type lanthanide-containing monolacunary Dawson-type tungstophosphates: [LnIII(α2-P2W17O61)2]17− (Ln = La, Ce). Dalton Trans. 2017, 46, 5398–5405.

Crossref Google Scholar
[52]

Tanuhadi, E.; Al-Sayed, E.; Roller, A.; Čipčić-Paljetak, H.; Verbanac, D.; Rompel, A. Synthesis, characterization, and phosphoesterase activity of a series of 4f- and 4d-sandwich-type germanotungstates [(n-C4H9)4N]l/mH2[(M(H2O)3)(γ-GeW10O35)2](M = CeIII, NdIII, GdIII, ErIII, l = 7; ZrIV, m = 6). Inorg. Chem. 2020, 59, 14078–14084.

Crossref Google Scholar
[53]

Wang, W. Y.; Izarova, N. V.; Van Leusen, J.; Kögerler, P. CeIII-functionalized polyoxotungstates: Discrete vs. extended architectures. Cryst. Growth Des. 2019, 19, 4860–4870.

Crossref Google Scholar
[54]

Liu, L. Z.; Li, F. Y.; Xu, L.; Liu, X. Z.; Gao, G. G. Magnetic relaxation behavior of lanthanide substituted Dawson-type tungstoarsenates. J. Solid State Chem. 2010, 183, 350–355.

Crossref Google Scholar
[55]

Huo, Y.; Chen, Y. C.; Wu, S. G.; Liu, J. L.; Jia, J. H.; Chen, W. B.; Wang, B. L.; Zhang, Y. Q.; Tong, M. L. Effect of bridging ligands on magnetic behavior in dinuclear dysprosium cores supported by polyoxometalates. Inorg. Chem. 2019, 58, 1301–1308.

Crossref Google Scholar
[56]

Ibrahim, M.; Baksi, A.; Peng, Y.; Al-Zeidaneen, F. K.; Mbomekalle, I. M.; De Oliveira, P.; Anson, C. E. Synthesis, characterization, electrochemistry, photoluminescence and magnetic properties of a dinuclear erbium(III)-containing monolacunary dawson-type tungstophosphate: [{Er(H2O)(CH3COO)(P2W17O61)}2]16−. Molecules 2020, 25, 4229.

Crossref Google Scholar
[57]

Liu, J. C.; Yu, J.; Han, Q.; Wen, Y.; Chen, L. J.; Zhao, J. W. First quadruple-glycine bridging mono-lanthanide-substituted borotungstate hybrids. Dalton Trans. 2016, 45, 16471–16484.

Crossref Google Scholar
[58]

Ma, P. T.; Hu, F.; Wu, H. C.; Liu, X. P.; Wang, J. P.; Niu, J. Y. Luminescent dimeric polyoxotungstate [Ho(C4H2O6)(α-PW11O39)]216− with magnetism and reversible photochromism. J. Lumin. 2020, 217, 116760.

Crossref Google Scholar
[59]

Niu, J. Y.; Wang, K. H.; Chen, H. N.; Zhao, J. W.; Ma, P. T.; Wang, J. P.; Li, M. X.; Bai, Y.; Dang, D. B. Assembly chemistry between lanthanide cations and monovacant keggin polyoxotungstates: Two types of lanthanide substituted phosphotungstates [{(α-PW11O39H)Ln(H2O)3}2]6− and [{(α-PW11O39)Ln(H2O)(η2,μ-1,1)-CH3COO}2]10−. Cryst. Growth Des. 2009, 9, 4362–4372.

Crossref Google Scholar
[60]

Wang, X. H.; Liu, Y. J.; Jin, M. T.; Wu, Y. X.; Chen, L. J.; Zhao, J. W. Two families of rare-earth-substituted dawson-type monomeric and dimeric phosphotungstates functionalized by carboxylic ligands. Cryst. Growth Des. 2017, 17, 5295–5308.

Crossref Google Scholar
[61]

Zhang, S. W.; Wang, Y.; Zhao, J. W.; Ma, P. T.; Wang, J. P.; Niu, J. Y. Two types of oxalate-bridging rare-earth-substituted Keggin-type phosphotungstates {[(α-PW11O39)RE(H2O)]2(C2O4)}10− and {(α-x-PW10O38)RE2(C2O4)(H2O)2}3−. Dalton Trans. 2012, 41, 3764–3772.

Crossref Google Scholar
[62]

Knoth, W. H.; Domaille, P. J.; Harlow, R. L. Heteropolyanions of the types M3(W9PO34)212− and MM'M''(W9PO34)212−: Novel coordination of nitrate and nitrite. Inorg. Chem. 1986, 25, 1577–1584.

Crossref Google Scholar
[63]

Tomsa, A. R.; Muresan, L.; Koutsodimou, A.; Falaras, P.; Rusu, M. Synthesis and characterisation of two new lanthanide sandwich-type heteropolyoxometalates. Polyhedron 2003, 22, 2901–2909.

Crossref Google Scholar
[64]

Giansiracusa, M. J.; Vonci, M.; Van Den Heuvel, W.; Gable, R. W.; Moubaraki, B.; Murray, K. S.; Yu, D. H.; Mole, R. A.; Soncini, A.; Boskovic, C. Carbonate-bridged lanthanoid triangles: Single-molecule magnet behavior, inelastic neutron scattering, and ab initio studies. Inorg. Chem. 2016, 55, 5201–5214.

Crossref Google Scholar
[65]

Khoshnavazi, R.; Gholamyan, S. Sandwich-type polyoxoanions based on A-β-GeW9O3410−. Synthesis and characterization of [(A-β-GeW9O34)2(MOH2)3CO3]13− (M = Y3+, Sm3+, and Yb3+) polyoxoanions. J. Coord. Chem 2010, 63, 3365–3372.

Crossref Google Scholar
[66]

Khoshnavazi, R.; Nicolò, F.; Rudbari, H. A.; Naseri, E.; Aminipour, A. Sandwich-type polyoxometalates of the later lanthanide ions. Syntheses and structures of [(A-XW9O34)2(H2OM)3CO3]11− (X = P5+, As5+) (M = Tb3+, Dy3+, Er3+). J. Coord. Chem 2013, 66, 1374–1383.

Crossref Google Scholar
[67]

Khoshnavazi, R. ; Sadeghi, R. ; Bahrami, L. High stable sandwich-type polyoxometallates based on A-β-SiW9O3410−. Synthesis, chemical properties and characterization of [(A-β-SiW9O34)2(MOH2)3CO3]13− (M = Y3+ and Yb3+). Polyhedron 2008, 27, 1855–1859.

Crossref Google Scholar
[68]

Kong, X. J.; Lin, Z. K.; Zhang, Z. M.; Zhang, T.; Lin, W. B. Hierarchical integration of photosensitizing metal-organic frameworks and nickel-containing polyoxometalates for efficient visible-light-driven hydrogen evolution. Angew. Chem., Int. Ed. 2016, 55, 6411–6416.

Crossref Google Scholar
[69]

Liu, Y. P.; Zhao, S. F.; Guo, S. X.; Bond, A. M.; Zhang, J.; Zhu, G. B.; Hill, C. L.; Geletii, Y. V. Electrooxidation of ethanol and methanol using the molecular catalyst [{Ru4O4(OH)2(H2O)4}(γ-SiW10O36)2]10−. J. Am. Chem. Soc. 2016, 138, 2617–2628.

Crossref Google Scholar
[70]

Lv, H. J.; Guo, W. W.; Wu, K. F.; Chen, Z. Y.; Bacsa, J.; Musaev, D. G.; Geletii, Y. V.; Lauinger, S. M.; Lian, T. Q.; Hill, C. L. A noble-metal-free, tetra-nickel polyoxotungstate catalyst for efficient photocatalytic hydrogen evolution. J. Am. Chem. Soc. 2014, 136, 14015–14018.

Crossref Google Scholar
[71]

Yin, Q. S.; Tan, J. M.; Besson, C.; Geletii, Y. V.; Musaev, D. G.; Kuznetsov, A. E.; Luo, Z.; Hardcastle, K. I.; Hill, C. L. A fast soluble carbon-free molecular water oxidation catalyst based on abundant metals. Science 2010, 328, 342–346.

Crossref Google Scholar
[72]

Dufaye, M.; Duval, S.; Nursiah, K.; Stoclet, G.; Trivelli, X.; Loiseau, T. Bottom-up synthesis of functionalized {Ce4(SiW9O34)2(L)2} polyoxometalates. CrystEngComm 2018, 20, 7144–7155.

Crossref Google Scholar
[73]

Duval, S.; Béghin, S.; Falaise, C.; Trivelli, X.; Rabu, P.; Loiseau, T. Stabilization of tetravalent 4f (Ce), 5d (Hf), or 5f (Th, U) clusters by the [α-SiW9O34]10− polyoxometalate. Inorg. Chem. 2015, 54, 8271–8280.

Crossref Google Scholar
[74]

Cai, Z. W.; Liu, B. X.; Yang, T.; Li, X. X.; Zheng, S. T. Syntheses and structures of the first two tetra-scandium substituted polyoxometalates. Inorg. Chem. Commun. 2017, 80, 1–5.

Crossref Google Scholar
[75]

Wang, Y.; Sun, X. P.; Li, S. Z.; Ma, P. T.; Wang, J. P.; Niu, J. Y. Synthesis and magnetic properties of tartrate-bridging rare-earth-containing polytungstoarsenate aggregates from an adaptive precursor [As2W19O67(H2O)]14−. Dalton Trans. 2015, 44, 733–738.

Crossref Google Scholar
[76]

Suzuki, K.; Tang, F.; Kikukawa, Y.; Yamaguchi, K.; Mizuno, N. Visible-light-induced photoredox catalysis with a tetracerium-containing silicotungstate. Angew. Chem., Int. Ed. 2014, 53, 5356–5360.

Crossref Google Scholar
[77]

Fang, X. K.; Anderson, T. M.; Benelli, C.; Hill, C. L. Polyoxometalate-supported Y- and YbIII-hydroxo/oxo clusters from carbonate-assisted hydrolysis. Chem.—Eur. J. 2005, 11, 712–718.

Crossref Google Scholar
[78]

Zhang, Y.; Li, Y. M.; Pang, J. J.; Liu, Y. F.; Li, P.; Chen, L. J.; Zhao, J. W. Two penta-REIII encapsulated tetravacant dawson selenotungstates and nanoscale derivatives and their luminescence properties. Inorg. Chem. 2019, 58, 7078–7090.

Crossref Google Scholar
[79]

Huo, Y. ; Chen, Y. C. ; Wu, S. G. ; Jia, J. H. ; Chen, W. B. ; Liu, J. L. ; Tong, M. L. pH-controlled assembly of organophosphonate-bridged dysprosium(III) single-molecule magnets based on polyoxometalates. Inorg. Chem 2018, 57, 6773–6777.

Crossref Google Scholar
[80]

Ma, P. T.; Wan, R.; Wang, Y. Y.; Hu, F.; Zhang, D. D.; Niu, J. Y.; Wang, J. P. Coordination-driven self-assembly of a 2D graphite-like framework constructed from high-nuclear Ce10 cluster encapsulated polyoxotungstates. Inorg. Chem. 2016, 55, 918–924.

Crossref Google Scholar
[81]

Ma, P. T.; Wan, R.; Si, Y. N.; Hu, F.; Wang, Y. Y.; Niu, J. Y.; Wang, J. P. Double-malate bridging tri-lanthanoid cluster encapsulated arsenotungstates: Syntheses, structures, luminescence and magnetic properties. Dalton Trans. 2015, 44, 11514–11523.

Crossref Google Scholar
[82]

Hao, Y.; Zhong, L.; Li, H. H.; Zheng, S. T. Two lanthanide-substituted polyoxometalates featuring novel crescent-shaped Ln5 clusters: Structures, ion conductivities, and magnetic properties. Cryst. Growth Des. 2019, 19, 1329–1335.

Crossref Google Scholar
[83]

Huo, Y.; Chen, Y. C.; Liu, J. L.; Jia, J. H.; Chen, W. B.; Wu, S. G.; Tong, M. L. A wheel-shaped Dy(III) single-molecule magnet supported by polyoxotungstates. Dalton Trans. 2017, 46, 16796–16801.

Crossref Google Scholar
[84]

Dufaye, M.; Duval, S.; Stoclet, G.; Loiseau, T. Influence of pH on CeIV-[AsIIIW9O33]9− association for the formation of hexanuclear cerium(IV) oxo-hydroxo-clusters stabilized by trivacant polyanions. CrystEngComm 2020, 22, 371–380.

Crossref Google Scholar
[85]

Duval, S.; Roussel, P.; Loiseau, T. Synthesis of a large dodecameric cerium cluster stabilized by the [SiW9O34]10− polyoxometalate. Inorg. Chem. Commun. 2017, 83, 52–54.

Crossref Google Scholar
[86]

Matsunaga, S.; Inoue, Y.; Mihara, K.; Nomiya, K. Synthesis and crystal structure of hexacerium(IV) cluster-containing Keggin polyoxometalate trimer. Inorg. Chem. Commun. 2017, 80, 61–64.

Crossref Google Scholar
[87]

Huo, Y.; Wan, R.; Ma, P. T.; Liu, J. L.; Chen, Y. C.; Li, D. D.; Niu, J. Y.; Wang, J. P.; Tong, M. L. Organophosphonate-bridged polyoxometalate-based dysprosium (III) single-molecule magnet. Inorg. Chem. 2017, 56, 12687–12691.

Crossref Google Scholar
[88]

Ma, X. Y.; He, P. P.; Xu, B. J.; Lu, J. K.; Wan, R.; Wu, H. C.; Wang, Y.; Ma, P. T.; Niu, J. Y.; Wang, J. P. Pyrazine dicarboxylate-bridged arsenotungstate: Synthesis, characterization, and catalytic activities in epoxidation of olefins and oxidation of alcohols. Dalton Trans. 2019, 48, 12956–12963.

Crossref Google Scholar
[89]

Ritchie, C.; Baslon, V.; Moore, E. G.; Reber, C.; Boskovic, C. Sensitization of lanthanoid luminescence by organic and inorganic ligands in lanthanoid-organic-polyoxometalates. Inorg. Chem. 2012, 51, 1142–1151.

Crossref Google Scholar
[90]

Ritchie, C.; Speldrich, M.; Gable, R. W.; Sorace, L.; Kögerler, P.; Boskovic, C. Utilizing the adaptive polyoxometalate [As2W19O67(H2O)]14- to support a polynuclear lanthanoid-based single-molecule magnet. Inorg. Chem. 2011, 50, 7004–7014.

Crossref Google Scholar
[91]

Xiong, J. ; Yang, Z. X. ; Ma, P. T. ; Lin, D. M. ; Zheng, Q. J. ; Huo, Y. pH-controlled assembly of two polynuclear Dy(III)-containing polytungstoarsenates with magnetic and luminescence properties. Inorg. Chem 2021, 60, 7519–7526.

Crossref Google Scholar
[92]

Chen, H. H.; Xiao, Z. K.; Yan, B.; Wu, H. C.; Ma, P. T.; Wang, J. P.; Niu, J. Y. H-shaped oxalate-bridging lanthanoid-incorporated arsenotungstates. Dalton Trans. 2020, 49, 15731–15738.

Crossref Google Scholar
[93]

Ma, P. T.; Hu, F.; Huo, Y.; Zhang, D. D.; Zhang, C.; Niu, J. Y.; Wang, J. P. Magnetoluminescent bifunctional dysprosium-based phosphotungstates with synthesis and correlations between structures and properties. Cryst. Growth Des. 2017, 17, 1947–1956.

Crossref Google Scholar
[94]

Howell, R. C.; Perez, F. G.; Jain, S.; Horrocks, W. D. Jr.; Rheingold, A. L. ; Francesconi, L. C. A new type of heteropolyoxometalates formed from lacunary polyoxotungstate ions and europium or yttrium cations. Angew. Chem., Int. Ed 2001, 40, 4031–4034.

Crossref Google Scholar
[95]

Hussain, F.; Gable, R. W.; Speldrich, M.; Kögerler, P.; Boskovic, C. Polyoxotungstate-encapsulated Gd6 and Yb10 complexes. Chem. Commun. (Camb.). 2009, 328–330

Crossref Google Scholar
[96]

Li, Z.; Li, X. X.; Yang, T.; Cai, Z. W.; Zheng, S. T. Four-shell polyoxometalates featuring high-nuclearity Ln26 clusters: Structural transformations of nanoclusters into frameworks triggered by transition-metal ions. Angew. Chem., Int. Ed. 2017, 56, 2664–2669.

Crossref Google Scholar
[97]

Liu, J. H.; Zhang, R. T.; Zhang, J.; Zhao, D.; Li, X. X.; Sun, Y. Q.; Zheng, S. T. A series of 3D porous lanthanide-substituted polyoxometalate frameworks based on rare hexadecahedral {Ln6W8O28} heterometallic cage-shaped cluster. Inorg. Chem. 2019, 58, 14734–14740.

Crossref Google Scholar
[98]

Wassermann, K.; Dickman, M. H.; Pope, M. T. Self-assembly of supramolecular polyoxometalates: The compact, water-soluble heteropolytungstate anion [AsⅢ12CeⅢ16(H2O)36W148O524]76−. Angew. Chem., Int. Ed. 1997, 36, 1445–1448.

Crossref Google Scholar
[99]

Jiang, J.; Liu, L. L.; Liu, G. P.; Wang, D.; Zhang, Y.; Chen, L. J.; Zhao, J. W. Organic-inorganic hybrid cerium-encapsulated selenotungstate including three building blocks and its electrochemical detection of dopamine and paracetamol. Inorg. Chem. 2020, 59, 15355–15364.

Crossref Google Scholar
[100]

Li, H. L.; Lian, C.; Chen, L. J.; Zhao, J. W.; Yang, G. Y. Two unusual nanosized Nd3+-substituted selenotungstate aggregates simultaneously comprising lacunary Keggin and Dawson polyoxotungstate segments. Nanoscale 2020, 12, 16091–16101.

Crossref Google Scholar
[101]

Li, H. L.; Liu, Y. J.; Li, Y. M.; Chen, L. J.; Zhao, J. W.; Yang, G. Y. Unprecedented selenium and lanthanide simultaneously bridging selenotungstate aggregates stabilized by four tetra-vacant dawson-like {Se2W14} units. Chem.—Asian J. 2018, 13, 2897–2907.

Crossref Google Scholar
[102]

Liu, J. L.; Wang, D.; Xu, X.; Li, H. L.; Zhao, J. W.; Chen, L. J. Multi-nuclear rare-earth-implanted tartaric acid-functionalized selenotungstates and their fluorescent and magnetic properties. Inorg. Chem. 2021, 60, 2533–2541.

Crossref Google Scholar
[103]

Liu, L. L.; Jiang, J.; Cui, L. M.; Zhao, J. W.; Cao, X. H.; Chen, L. J. Double trigonal pyramidal {SeO3} groups bridged 2-picolinic acid modified cerium-inlaid polyoxometalate including mixed selenotungstate subunits for electrochemically sensing ochratoxin A. Inorg. Chem. 2022, 61, 1949–1960.

Crossref Google Scholar
[104]

Liu, Y. J.; Li, H. L.; Lu, C. T.; Gong, P. J.; Ma, X. Y.; Chen, L. J.; Zhao, J. W. Organocounterions-assisted and pH-controlled self-assembly of five nanoscale high-nuclear lanthanide substituted heteropolytungstates. Cryst. Growth Des. 2017, 17, 3917–3928.

Crossref Google Scholar
[105]

Zhang, Y.; Jiang, J.; Liu, Y. F.; Li, P.; Liu, Y.; Chen, L. J.; Zhao, J. W. Multi-praseodymium-and-tungsten bridging octameric tellurotungstate and its 2D honeycomb composite film for detecting estrogen. Nanoscale 2020, 12, 10842–10853.

Crossref Google Scholar
[106]

Liu, L. L.; Jiang, J.; Liu, X. Y.; Liu, G. P.; Wang, D.; Chen, L. J.; Zhao, J. W. First series of mixed (PIII, SeIV)-heteroatomoriented rare-earth-embedded polyoxotungstates containing distinct building blocks. Inorg. Chem. Front. 2020, 7, 4640–4651.

Crossref Google Scholar
[107]

Han, L. Z.; Jiao, C. Q.; Chen, W. C.; Shao, K. Z.; Jin, L. Y.; Su, Z. M. Assembly of tetra-nuclear YbIII-containing selenotungstate clusters: Synthesis, structures, and magnetic properties. Dalton Trans. 2021, 50, 11535–11541.

Crossref Google Scholar
[108]

Chen, W. C.; Yan, L. K.; Wu, C. X.; Wang, X. L.; Shao, K. Z.; Su, Z. M.; Wang, E. B. Assembly of keggin-/dawson-type polyoxotungstate clusters with different metal units and SeO32- heteroanion templates. Cryst. Growth Des. 2014, 14, 5099–5110.

Crossref Google Scholar
[109]

Han, Q.; Wen, Y.; Liu, J. C.; Zhang, W.; Chen, L. J.; Zhao, J. W. Rare-earth-incorporated tellurotungstate hybrids functionalized by 2-picolinic acid ligands: Syntheses, structures, and properties. Inorg. Chem. 2017, 56, 13228–13240.

Crossref Google Scholar
[110]

Li, H. L.; Liu, Y. J.; Zheng, R.; Chen, L. J.; Zhao, J. W.; Yang, G. Y. Trigonal pyramidal {AsO2(OH)} bridging tetranuclear rare-earth encapsulated polyoxotungstate aggregates. Inorg. Chem. 2016, 55, 3881–3893.

Crossref Google Scholar
[111]

Li, H. L.; Lian, C.; Chen, L. J.; Zhao, J. W.; Yang, G. Y. Two Ce3+-substituted selenotungstates regulated by N,N-dimethylethanolamine and dimethylamine hydrochloride. Inorg. Chem. 2019, 58, 8442–8450.

Crossref Google Scholar
[112]

Li, H. L.; Liu, Y. J.; Liu, J. L.; Chen, L. J.; Zhao, J. W.; Yang, G. Y. Structural transformation from dimerization to tetramerization of serine-decorated rare-earth-incorporated arsenotungstates induced by the usage of rare-earth salts. Chem.—Eur. J. 2017, 23, 2673–2689.

Crossref Google Scholar
[113]

Li, Y. M.; Li, H. L.; Jiang, J.; Chen, L. J.; Zhao, J. W. Three types of distinguishing L-alanine-decorated and rare-earth-incorporated arsenotungstate hybrids prepared in a facile one-step assembly strategy. Inorg. Chem. 2019, 58, 3479–3491.

Crossref Google Scholar
[114]

Shang, S. X.; Lin, Z. G.; Yin, A. X.; Yang, S.; Chi, Y. N.; Wang, Y.; Dong, J.; Liu, B.; Zhen, N.; Hill, C. L. et al. Self-assembly of Ln(III)-containing tungstotellurates(VI): Correlation of structure and photoluminescence. Inorg. Chem. 2018, 57, 8831–8840.

Crossref Google Scholar
[115]

Wang, D.; Li, Y. M.; Zhang, Y.; Xu, X.; Liu, Y.; Chen, L. J.; Zhao, J. W. Construction of Ln3+-substituted arsenotungstates modified by 2,5-thiophenedicarboxylic acid and application in selective fluorescence detection of Ba2+ in aqueous solution. Inorg. Chem. 2020, 59, 6839–6848.

Crossref Google Scholar
[116]

Wang, Y. J.; Wu, S. Y.; Sun, Y. Q.; Li, X. X.; Zheng, S. T. Octahedron-shaped three-shell Ln14-substituted polyoxotungstogermanates encapsulating a W4O15 cluster: Luminescence and frequency dependent magnetic properties. Chem. Commun. (Camb.) 2019, 55, 2857–2860.

Crossref Google Scholar
[117]

Zhang, Y.; Wang, D.; Zeng, B. X.; Chen, L. J.; Zhao, J. W.; Yang, G. Y. An unprecedented polyhydroxycarboxylic acid ligand bridged multi-EuIII incorporated tellurotungstate and its luminescence propertie. Dalton Trans. 2020, 49, 8933–8948.

Crossref Google Scholar
[118]

Du, M. H.; Zheng, X. Y.; Kong, X. J.; Long, L. S.; Zheng, L. S. Synthetic protocol for assembling giant heterometallic hydroxide clusters from building blocks: Rational design and efficient synthesis. Matter 2020, 3, 1334–1349.

Crossref Google Scholar
[119]

Fang, X. K.; Kögerler, P. A polyoxometalate-based manganese carboxylate cluster. Chem. Commun. (Camb.) 2008, 3396–3398

Crossref Google Scholar
[120]

Fang, X. K.; Kögerler, P. PO43−-mediated polyoxometalate supercluster assembly. Angew. Chem., Int. Ed. 2008, 47, 8123–8126.

Crossref Google Scholar
[121]

Chen, W. L.; Li, Y. G.; Wang, Y. H.; Wang, E. B.; Zhang, Z. M. A new polyoxometalate-based 3d-4f heterometallic aggregate: A model for the design and synthesis of new heterometallic clusters. Dalton Trans. 2008, 865–867

Crossref Google Scholar
[122]

Gu, Y. N.; Yu, H.; Lin, L. D.; Wu, Y. L.; Li, Z.; Pan, W. Y.; He, J.; Chen, L.; Li, Q.; Li, X. X. Two rare Cr-Ln (Ln = Dy, Tb) heterometallic cluster substituted polyoxometalates featuring hexameric aggregates: Hydrothermal syntheses, crystal structures and magnetic studies. New J. Chem. 2019, 43, 3011–3016.

Crossref Google Scholar
[123]

Wang, J.; Zhao, J. W.; Zhao, H. Y.; Yang, B. F.; He, H.; Yang, G. Y. Syntheses, structures and properties of two multi-iron-samarium/multi-iron substituted germanotungstates. CrystEngComm 2014, 16, 252–259.

Crossref Google Scholar
[124]

Zhang, Z. M.; Li, Y. G.; Yao, S.; Wang, E. B. Hexameric polyoxometalates decorated by six 3d-4f heterometallic clusters. Dalton Trans. 2011, 40, 6475–6479.

Crossref Google Scholar
[125]

Ibrahim, M.; Krämer, S.; Schork, N.; Guthausen, G. Polyoxometalate-based high-spin cluster systems: A NMR relaxivity study up to 14 GHz/33 T. Dalton Trans. 2019, 48, 15597–15604.

Crossref Google Scholar
[126]

Ibrahim, M.; Mereacre, V.; Leblanc, N.; Wernsdorfer, W.; Anson, C. E.; Powell, A. K. Self-assembly of a giant tetrahedral 3d-4f single-molecule magnet within a polyoxometalate system. Angew. Chem., Int. Ed. 2015, 54, 15574–15578.

Crossref Google Scholar
[127]

Ibrahim, M.; Peng, Y.; Moreno-Pineda, E.; Anson, C. E.; Schnack, J.; Powell, A. K. Gd3 triangles in a polyoxometalate matrix: Tuning molecular magnetocaloric effects in {Gd30M8} polyoxometalate/cluster hybrids through variation of M2+. Small Struct. 2021, 2, 2170029.

Crossref Google Scholar
[128]

Reinoso, S.; Galán-Mascarós, J. R.; Lezama, L. New type of heterometallic 3d-4f rhomblike core in weakley-like polyoxometalates. Inorg. Chem. 2011, 50, 9587–9593.

Crossref Google Scholar
[129]

Nohra, B.; Mialane, P.; Dolbecq, A.; Rivière, E.; Marrot, J.; Sécheresse, F. Heterometallic 3d-4f cubane clusters inserted in polyoxometalate matrices. Chem. Commun. (Camb.) 2009, 2703–2705

Crossref Google Scholar
[130]

Wang, W. D.; Li, X. X.; Fang, W. H.; Yang, G. Y. Hydrothermal synthesis and structural characterization of a new keggin-type tungstogermanate containing heterometallic 3d-4f cubane clusters. J. Cluster Sci. 2011, 22, 87–95.

Crossref Google Scholar
[131]

Wang, Y. F.; Qin, Z. J.; Tian, Z. F.; Bai, Y.; Li, Y. M.; Zhang, Y. W.; Dang, D. B. A series of germanotungstate-based 3d-4f heterometallic compounds with visible-light induced photocatalytic, electrochemical and magnetic properties. J. Alloys Compd. 2019, 784, 961–969.

Crossref Google Scholar
[132]

Zhao, J. W.; Shi, D. Y.; Chen, L. J.; Li, Y. Z.; Ma, P. T.; Wang, J. P.; Niu, J. Y. Novel polyoxometalate hybrids consisting of copper-lanthanide heterometallic/lanthanide germanotungstate fragments. Dalton Trans. 2012, 41, 10740–10751.

Crossref Google Scholar
[133]

Cai, J.; Zheng, X. Y.; Xie, J.; Yan, Z. H.; Kong, X. J.; Ren, Y. P.; Long, L. S.; Zheng, L. S. Anion-dependent assembly of heterometallic 3d-4f clusters based on a lacunary polyoxometalate. Inorg. Chem. 2017, 56, 8439–8445.

Crossref Google Scholar
[134]

Li, S. R.; Wang, H. Y.; Su, H. F.; Chen, H. J.; Du, M. H.; Long, L. S.; Kong, X. J.; Zheng, L. S. A giant 3d-4f polyoxometalate super-tetrahedron with high proton conductivity. Small Methods 2021, 5, 2000777.

Crossref Google Scholar
[135]

Wu, S. Y.; Wang, Y. J.; Jing, J. X.; Li, X. X.; Sun, Y. Q.; Zheng, S. T. Two organic-inorganic hybrid polyoxotungstogermanates containing organic ligand chelated Fe-Dy heterometallic clusters and frequency dependent magnetic properties. Inorg. Chem. Front. 2020, 7, 498–504.

Crossref Google Scholar
[136]

Chen, Y.; Guo, Z. W.; Li, X. X.; Zheng, S. T.; Yang, G. Y. Multicomponent cooperative assembly of nanoscale boron-rich polyoxotungstates with 22 and 30 boron atoms. CCS Chem. 2022, 4, 1305–1314.

Crossref Google Scholar
[137]

Chen, C. H.; Chen, Y.; Yao, R. Q.; Li, Y. X.; Zhang, C. X. Artificial Mn4Ca clusters with exchangeable solvent molecules mimicking the oxygen-evolving center in photosynthesis. Angew. Chem., Int. Ed. 2019, 58, 3939–3942.

Crossref Google Scholar
[138]

Chen, Y. Z.; Liu, Z. J.; Zhang, Z. M.; Zhou, H. Y.; Zheng, X. T.; Wang, E. B. Systematic assembly of {LnMnIII4} appended cubanes with inorganic polyoxometalate ligands and their electrocatalytic property. Inorg. Chem. Commun. 2014, 46, 155–158.

Crossref Google Scholar
[139]

Yao, R. Q.; Li, Y. X.; Chen, Y.; Xu, B. R.; Chen, C. H.; Zhang, C. X. Rare-earth elements can structurally and energetically replace the calcium in a synthetic Mn4CaO4-cluster mimicking the oxygen-evolving center in photosynthesis. J. Am. Chem. Soc. 2021, 143, 17360–17365.

Crossref Google Scholar
[140]

Chen, L. J.; Zhang, F.; Ma, X.; Luo, J.; Zhao, J. W. Two types of novel tetra-iron substituted sandwich-type arsenotungastates with supporting lanthanide pendants. Dalton Trans. 2015, 44, 12598–12612.

Crossref Google Scholar
[141]

Das, V.; Khan, I.; Hussain, F.; Sadakane, M.; Tsunoji, N.; Ichihashi, K.; Kato, C.; Inoue, K.; Nishihara, S. Single-molecule magnetic, catalytic and photoluminescence properties of heterometallic 3d-4f [Ln{PZn2W10O38(H2O)2}2]11− tungstophosphate nanoclusters. Eur. J. Inorg. Chem. 2021, 2021, 3819–3831.

Crossref Google Scholar
[142]

Jiang, J.; Chen, Y. H.; Liu, L. L.; Chen, L. J.; Zhao, J. W. 2-Picolinate-decorated iron-lanthanide heterometallic germanotungstates including an S-shaped [Ge2W20O72]16− segment. Inorg. Chem. 2019, 58, 15853–15863.

Crossref Google Scholar
[143]

Li, S. R.; Weng, Z. Z.; Jiang, L. P.; Wei, R. J.; Su, H. F.; Long, L. S.; Zheng, L. S.; Kong, X. J. A series of heterometallic 3d-4f polyoxometalates as single-molecule magnets. Chin. Chem. Lett. 2023, 34, 107251–107254.

Crossref Google Scholar
[144]

Minato, T.; Salley, D.; Mizuno, N.; Yamaguchi, K.; Cronin, L.; Suzuki, K. Robotic stepwise synthesis of hetero-multinuclear metal oxo clusters as single-molecule magnets. J. Am. Chem. Soc. 2021, 143, 12809–12816.

Crossref Google Scholar
[145]

Sato, R.; Suzuki, K.; Minato, T.; Yamaguchi, K.; Mizuno, N. Sequential synthesis of 3d-3d′-4f heterometallic heptanuclear clusters in between lacunary polyoxometalates. Inorg. Chem. 2016, 55, 2023–2029.

Crossref Google Scholar
[146]

Zhu, S. L.; Xu, X.; Ou, S.; Zhao, M.; He, W. L.; Wu, C. D. Assembly of a metalloporphyrin-polyoxometalate hybrid material for highly efficient activation of molecular oxygen. Inorg. Chem. 2016, 55, 7295–7300.

Crossref Google Scholar
[147]

Zhao, J. W.; Cao, J.; Li, Y. Z.; Zhang, J.; Chen, L. J. First tungstoantimonate-based transition-metal-lanthanide heterometallic hybrids functionalized by amino acid ligands. Cryst. Growth Des. 2014, 14, 6217–6229.

Crossref Google Scholar
[148]

Cai, J.; Ye, R.; Liu, X. H.; Guo, L. L.; Qiao, X. R. Ionic strength effect on regulating the synthetic assembly of polyoxometalate clusters with slow magnetic relaxation behavior. Dalton Trans. 2020, 49, 16954–16961.

Crossref Google Scholar
[149]

Das, V.; Khan, I.; Hussain, F.; Sadakane, M.; Hageo, K.; Ichihashi, K.; Inoue, K.; Nishihara, S. A self-assembled heterometallic {Co7-Ho1} nanocluster: 3d-4f trimeric keggin-type silicotungstate [HoCo7Si3W29O108(OH)5(H2O)4]18− and its catalytic and magnetic applications. Eur. J. Inorg. Chem. 2019, 2019, 430–436.

Crossref Google Scholar
[150]

Tanuhadi, E.; Al-Sayed, E.; Novitchi, G.; Roller, A.; Giester, G.; Rompel, A. Cation-directed synthetic strategy using 4f tungstoantimonates as nonlacunary precursors for the generation of 3d-4f clusters. Inorg. Chem. 2020, 59, 8461–8467.

Crossref Google Scholar
[151]

Gu, Y. N.; Chen, Y.; Wu, Y. L.; Zheng, S. T.; Li, X. X. A series of banana-shaped 3d-4f heterometallic cluster substituted polyoxometalates: Syntheses, crystal structures, and magnetic properties. Inorg. Chem. 2018, 57, 2472–2479.

Crossref Google Scholar
[152]

Han, Q.; Li, Z.; Liang, X. M.; Ding, Y.; Zheng, S. T. Synthesis of a 6-nm-long transition-metal-rare-earth-containing polyoxometalate. Inorg. Chem. 2019, 58, 12534–12537.

Crossref Google Scholar
[153]

Yao, M. Y.; Liu, Y. F.; Li, X. X.; Yang, G. P.; Zheng, S. T. The largest Se-4f cluster incorporated polyoxometalate with high Lewis acid-base catalytic activity. Chem. Commun. (Camb.) 2022, 58, 5737–5740.

Crossref Google Scholar
[154]

Xiao, H. P.; Zhang, R. T.; Li, Z.; Xie, Y. F.; Wang, M.; Ye, Y. D.; Sun, C.; Sun, Y. Q.; Li, X. X.; Zheng, S. T. Organoamine-directed assembly of 5p-4f heterometallic cluster substituted polyoxometalates: Luminescence and proton conduction properties. Inorg. Chem. 2021, 60, 13718–13726.

Crossref Google Scholar
[155]

Xu, X.; Chen, Y. H.; Zhang, Y.; Liu, Y. F.; Chen, L. J.; Zhao, J. W. Rare-earth and antimony-oxo clusters simultaneously connecting antimonotungstates comprising divacant and tetravacant keggin fragments. Inorg. Chem. 2019, 58, 11636–11648.

Crossref Google Scholar
[156]

Li, H. L.; Xu, X.; Tang, Z. G.; Zhao, J. W.; Chen, L. J.; Yang, G. Y. Three lanthanide-functionalized antimonotungstate clusters with a {Sb4O4Ln3(H2O)8} core: Syntheses, structures, and properties. Inorg. Chem. 2021, 60, 18065–18074.

Crossref Google Scholar
[157]

Xiao, H. P.; Hao, Y. S.; Li, X. X.; Xu, P.; Huang, M. D.; Zheng, S. T. A water-soluble antimony-rich polyoxometalate with broad-spectrum antitumor activities. Angew. Chem., Int. Ed. 2022, 61, e202210019.

Crossref Google Scholar
[158]

Xu, X. ; Liu, X. Y. ; Wang, D. ; Liu, X. J. ; Chen, L. J. ; Zhao, J. W. {HPO3} and {WO4} simultaneously induce the assembly of tri-Ln(III)-incorporated antimonotungstates and their photoluminescence behaviors. Inorg. Chem 2021, 60, 1037–1044.

Crossref Google Scholar
[159]

Xu, X.; Meng, R. R.; Lu, C. T.; Mei, L.; Chen, L. J.; Zhao, J. W. Acetate-decorated tri-Ln(III)-containing antimonotungstates with a tetrahedral {WO4} group as a structure-directing template and their luminescence properties. Inorg. Chem. 2020, 59, 3954–3963.

Crossref Google Scholar
[160]

Shao, D.; Wang, X. Y. Development of single-molecule magnets. Chin. J. Chem. 2020, 38, 1005–1018.

Crossref Google Scholar
[161]

Cardona-Serra, S.; Clemente-Juan, J. M.; Coronado, E.; Gaita-Ariño, A.; Camón, A.; Evangelisti, M.; Luis, F.; Martínez-Pérez, M. J.; Sesé, J. Lanthanoid single-ion magnets based on polyoxometalates with a 5-fold symmetry: The series [LnP5W30O110]12- (Ln3+ = Tb, Dy, Ho, Er, Tm, and Yb). J. Am. Chem. Soc. 2012, 134, 14982–14990.

Crossref Google Scholar
[162]

Liu, J. L.; Chen, Y. C.; Tong, M. L. Symmetry strategies for high performance lanthanide-based single-molecule magnets. Chem. Soc. Rev. 2018, 47, 2431–2453.

Crossref Google Scholar
[163]

AlDamen, M. A.; Clemente-Juan, J. M.; Coronado, E.; Martí-Gastaldo, C.; Gaita-Ariño, A. Mononuclear lanthanide single-molecule magnets based on polyoxometalates. J. Am. Chem. Soc. 2008, 130, 8874–8875.

Crossref Google Scholar
[164]

Osamu, N.; Teruo, K.; Isao, O.; Yoshizo, M. High-conductivity solid proton conductors: Dodecamolybdophosphoric acid and dodecatungstophosphoric acid crystals. Chem. Lett. 1979, 8, 17–18.

Crossref Google Scholar
[165]

Liu, J. C.; Han, Q.; Chen, L. J.; Zhao, J. W.; Streb, C.; Song, Y. F. Aggregation of giant cerium-bismuth tungstate clusters into a 3D porous framework with high proton conductivity. Angew. Chem., Int. Ed. 2018, 57, 8416–8420.

Crossref Google Scholar
Polyoxometalates
Volume 2 Issue 2,
June 2023
Article number: 9140022
DOI: 10.26599/POM.2023.9140022
Cite this article:
Li S-R, Liu W-D, Long L-S, et al. Recent advances in polyoxometalate-based lanthanide–oxo clusters. Polyoxometalates, 2023, 2(2): 9140022. https://doi.org/10.26599/POM.2023.9140022
Metrics & Citations  
Article History
Copyright
Rights and Permissions
Return

Details of the “pure 4f clusters” involved in the manuscripta

LnOCsLogogramIconSynthetic methods
a In the synthetic methods column: 1 stands for “lacunary POMs ligand-directed method”, 2 stands for “in-situ transformation lacunary POMs ligand directed method”, and 3 stands for “in-situ generation lacunary POMs ligand-directed method”. In the “Logogram” column, the ratio indicates the NLn3+:NPOMs of the clusters.
[Ln(H2O)nGeW11O39]5− (Ln = Dy, Er, n = 4, 3) [47][LnGeW11] (1:1)—2
[LnH(PW11O39)(phen)2]3− (Ln = Dy, Er) [48][LnPW11] (1:1)—1
[Ln(α-P2W17O61)2]17− (Ln = La, Ce) [49][Ln(P2W17)2] (1:2)Fig. 1(a)2
[Ln(β2-GeW11O39)2]13− (Ln = La, Ce, Pr, Nd, Sm, Gd, Dy) [50][Ln(GeW11)2] (1:2)Fig. 1(b)1
[Ln(β2-GeW11O39)(α-GeW11O39)]13− (Ln = Ho, Er, Tm) [51][Ln(GeW11)2] (1:2)Fig. 1(b)1
[Eu(α-GeW11O39)2]13− [49][EuGeW11] (1:2)Fig. 1(c)3
[Ln(H2O)3(GeW10)2]9− (Ln = Ce, Nd, Gd, Er) [52][Ln(GeW10)2] (1:2)Fig. 1(d)1
[{Ce(H2O)3(α2-P2W17O61)}2]14− [53][(CeP2W17)2] (2:2)Fig. 2(a)2
[{Ln(H2O)2(α2-As2W17O61)}2]14− (Ln = Dy, Er) [54][(LnAs2W17)2] (2:2)Fig. 2(b)2
[Ln2(H2ox)2(ox)(α2-P2W17O61)2]16− (Ln = Ho, Er, Tm, Yb, Y; H2ox = oxalic acid) [55][(LnP2W17)2] (2:2)Fig. 2(c)2
[{Er(H2O)(CH3COO)(P2W17O61)}2]16− [56][(ErP2W17)2] (2:2)Fig. 2(d)1
[(PW11O39)2Dy2X2(H2O)2]10− (X = –OH, F−, OAc−) [57][(DyPW11)2] (2:2)Fig. 2(e)2
[Ln(C4H2O6)(α-PW11O39)]216− ( Ln = Dy, Ho, Er, Yb, Tm) [58][(LnPW11)2] (2:2)Fig. 2(f)2
[Ln2(Gly)4(α-BW11O39)2]12− (Ln = Ce, Pr, Nd, Sm, Eu, Tm; Gly = glycine) [59][(LnBW11)2] (2:2)Fig. 2(g)1
{[(α-PW11O39)Ln(H2O)]2(C2O4)}10− (Ln = Y, Dy, Ho, Er) [60][(LnPW11)2] (2:2)Fig. 2(h)1
[{Ln(α-SiW11O39)(H2O)}2(CH3COO)2]12− (Ln = Eu, Gd, Tb, Dy, Ho, Er, Tm) [61][(LnSiW11)2] (2:2)Fig. 2(i)2
[(PW9O34)2Ce3O3(H2O)2]12− [62][Ce3(PW9)2] (3:2)Fig. 3(a)1
{[Ln3O3(OH2)2](PW9O34)2}15− (Ln = La, Ce) [63][Ln3(PW9)2] (3:2)Fig. 3(a)1
[(YOH2)3(CO3)(A-α-PW9O34)2]11− [64][Y3(PW9)2] (3:2)Fig. 3(b)1
[(LnOH2)3(CO3)(PW9O34)2]11− (Ln = Y, Tb, Dy, Ho, Er) [64][Ln3(PW9)2] (3:2)Fig. 3(b)1
[(SiW9O34)2(LnH2O)3CO3]13− (Ln = Y, Yb) [66][Ln3(SiW9)2] (3:2)Fig. 3(c)1
[((GeW9O34)2(LnH2O)3CO3]13− (Ln = Y, Sm, Yb) [65][Ln3(GeW9)2] (3:2)Fig. 3(c)1
[(AsW9O34)2(LnH2O)3CO3]11− (Ln = Tb, Dy, Er) [67][Ln3(AsW9)2] (3:2)Fig. 3(b)1
[Ce4(μ3-O)2(SiW9O34)2(C5H8O2NH3)2]8− [72][Ce4(SiW9)2] (4:2)Fig. 4(a)1
[Ce4(μ3-O)2(SiW9O34)2(CH3COO)2]10− [73][Ce4(SiW9)2] (4:2)Fig. 4(b)1
[Ce4(μ3-O)2(SiW9O34)2(C4H5O4)2]10− [72][Ce4(SiW9)2] (4:2)—1
[Ce4(μ3-O)2(SiW9O34)2(C5H7O4)2]10− [72][Ce4(SiW9)2] (4:2)—1
[Ce4(μ3-O)2(SiW9O34)2(C6H10O2NH3)2]8− [72][Ce4(SiW9)2] (4:2)—1
[Ln2(C4H4O6)(C4H2O6)(AsW9O33)]218− (Ln = Ho, Er, Tm, Yb. Lu, Y) [75][(Ln2AsW9)2] (4:2)Fig. 4(c)2
[Sc4(H2O)10(B-β-SbW9O33)2]6− [74][Sc4(SbW9)2] (4:2)Fig. 4(d)1
[{Ce(H2O)}2{Ce(CH3CN)}2(μ4-O)(SiW10O36)2]6− [76][Ce4(SiW10)2] (4:2)Fig. 4(e)1
[{Y4(μ3-OH)4(H2O)8(a-P2W15O56)2]16− [77][Y4(P2W15)2] (4:2)Fig. 4(f)1
[SeO4Ln5(H2O)7(Se2W14O52)2]13− (Ln = Tb, Dy, Gd, Ho, Er, Tm) [78][Ln5(Se2W14)2] (5:2)Fig. 5(a)3
[Dy6(ampH)4(H2O)23(ampH2)(PW11O39)2] [79][Dy6(PW11) 2] (6:2)Fig. 5(b)2
[{Yb6(μ6-O)2(μ3-OH)6(H2O)6(a-P2W15O56)2]14− [77][Yb6(P2W15)2] (6:2)Fig. 5(c)1
[CeIV7CeIII3O6(OH)6(CO3)(H2O)11(P2W16O59)3]19− [80][Ce10(P2W16)3] (10:3)Fig. 6(a)2
{[Ln3(μ3-OH)(H2O)8(AsW9O33)(AsW10O35(mal)]2}22− (Ln = Sm, Eu, Gd, Tb, Dy, Er; mal = malate) [81][Ln3(AsW9)(AsW10)]2 (3:2)Fig. 6(b)2
{Ln10(μ3-OH)2(H2O)10[α(1,8)-GeW10O38]2[β(4,11)-GeW10O38]2}20− ( Ln = La, Ce) [82][Ln10(GeW10)4] (10:4)Fig. 6(c)2
[Dy9(CO3)3(ampH)2(H2O)12(PW10O37)6]35− [79][Dy3(PW10)2]3 (9:6)Fig. 7(a)2
[{(AsW9O33)Dy(H2O)2}6]36− [83][(DyAsW9)6] (6:6)Fig. 7(b)2
[{Ce6(μ3-O)4(μ3-OH)4(OAc)2}(A-α-SiW9O34)2(α-SiW11O39)]18− [86][Ce6(SiW9)2(SiW11)] (6:3)Fig. 8(a)2
[(W4O10){(Ce6(μ3-O)5(μ4-O)3(μ2-H2O))(AsVW9O34)3}2]44− (Ce12-2) [84][Ce12(AsW9)6] (12:6)Fig. 8(b)1
{[Ce6(μ3-O)4(μ3-OH)3]2-(μ4-O)2(CH3COO)13(SiW9O34)2}11− (Ce12-1) [85][(Ce6)2(SiW9)2] (12:2)Fig. 8(c)1
[(Ce6(μ4-O)3(μ3-O)5(μ2-H2O)3)(HCOO)3(AsVW9O34)3]22− (Ce6-2) [84][Ce6(AsW9)3] (6:3)Fig. 8(d)1
[{Ce6(μ3-O)4(μ3-OH)4(HCOO)3.5}4(AsIIIW9O33)4]2− (Ce24) [84][(Ce6AsW9)4] (24:4)Fig. 8(e)1
[(Ce6(μ3-O)4(μ3-OH)4)(H2O)4(AsIIIW9O33)(HCOO)9]6− (Ce6-1) [84][Ce6AsW9] (6:1)Fig. 8(f)1

Details of the POMs-based “5d–4f clusters” involved in the manuscript

LnOCsLogogramIconSynthetic methodsa
a 1 stands for “lacunary POMs ligand-directed method”, 2 stands for “in-situ transformation lacunary POMs ligand directed method”, and 3 stands for “in-situ generation lacunary POMs ligand-directed method”.
[(AsW9O33)6Dy6W10O24(H2O)23]24− [91][Dy6W10(AsW9)6]Fig. 9(a)2
[(AsW9O33)7Dy7W8O21(H2O)17(μ3-OH)(OH)]38− [91][Dy7W8(AsW9)7]Fig. 9(b)2
[Ln4As5W40O144(H2O)10(Gly)2]21− (Ln = Gd, Tb, Dy, Ho, Y) [90][Ln4W4(AsW9)4]Fig. 9(c)2
[Tb2(pic)(H2O)2(B-β-AsW8O30)2(WO2(pic))3]10− [89][Tb2W3(AsW8)2]—2
[Ln8(pic)6(H2O)22(B-β-AsW8O30)4(WO2(pic))6]12− (Ln = Tb, Eu) [89][Ln8W12(AsW8)4]Fig. 9(d)2
{[Pr2(H2O)3(pzdc)As3W29O103]2}32− [88][Pr2W2(AsW9)3]2Fig. 9(e)2
[{(AsW9O33)3Dy2(H2O)4W4O9(H2O)}2(NH2(CH2PO3)2)]33− [87][Dy2W4(AsW9)3]2Fig. 9(f)2
[Dy8(PW10O38)4(OH)4(H2O)2(W3O14)]26− [93][Dy8W7(PW9)4]Fig. 10(a)2
[Ln8(PW9O34)4(W7O30)]30− (Ln = Eu, Y) [94][Ln8W7(PW9)4]Fig. 10(b)2
[Gd6As6W65O229(OH)4(H2O)12(OAc)2]38− [95][Gd6W11(AsW9)6]Fig. 11(b)2
[Yb10As10W88O308(OH)8(H2O)28(OAc)4]40− [95][Yb10W16(AsW9)8]Fig. 11(c)2
[Ln27Ge10W106O406 (OH)4(H2O)24]59− (Ln = La, Ce) [96][Ln@W6@Ln26@(GeW10)10]Fig. 12(a)2
{[Ln3(H2O)3(α-SiW11O39)2]2}14− (Ln = Sm, Eu, Gd, Tb, Dy) [97][Ln6W8(SiW9)4]Fig. 12(b)2
[AsIII12CeIII16(H2O)36W148O524]76− [98][Ce16W20(W5O18)4(AsW9)12]Fig. 12(c)3
{[Ce3W4O10(H2O)9(CH3COO)3]2(Se2W7O30)(B-α-SeW9O33)4}22− [99][(Ce3W4)2W7(SeW9)4]Fig. 13(a)3
{[Se2Ce4(H2O)8W4(HPIC)4O10][B-β-SeW8O30]2[Se2W12O46]2}16− [103][Ce2W2(Se2W12)(SeW8)]2Fig. 13(b)3
{[W2O5(OH)2(H2tart)2](H2tart){[W3O6Ln2(H2O)6][SeW9O33]2}2}14− (Ln = Eu, Tb, Dy, Ho, Y; H4tart = D-tartaric acid) [102]{[Ln2W3(SeW9)2]2W2}Fig. 13(c)3
{[W3Nd2(H2O)3(NO3)O6](B-α-SeW9O33)2(α-Se2W14O52)}17− [100][Nd2W3(Se2W14)(SeW9)]Fig. 13(d)3
{[W2Nd2(H2O)8O6(OH)2(β-Se2W14O52)][W3Nd2(H2O)6O7(B-α-SeW9O33)2]2}20− [100][W5Nd4(Se2W14)][Nd2W3(SeW9)]2Fig. 13(e)3
{[W16Ln10(H2O)38O50][B-α-SeW9O33]8}38− (Ln = La, Ce) [104][Ln10W16(SeW9)8]Fig. 13(f)3
{[W18Ln10(H2O)34O56][B-α-SeW9O33]8}38− (Ln = La, Ce) [104][Ln10W18(SeW9)8]Fig. 13(g)3
[W16Nd10O50(H2O)34(B-α-AsW9O33)8]40− [104][Nd10W16(AsW9)8]Fig. 13(f)3
[W16Pr8O48(H2O)20(B-α-TeW9O33)8]40− [105][Pr8W16(TeW9)8]Fig. 13(h)3
[Ln2(H2O)7(W4O9)(HPSeW15O54)(SeW9O33)2]14− (Ln = Ce, Pr, Nd, Sm, Gd, Tb, Ho, Er) [106][Ln2W4(PSeW15)(SeW9)]Fig. 13(i)3
{[Ln4W4Se4O22(H2O)5](Se2W14O52)2}232− (Ln = Tb, Dy, Ho, Er, Tm, Yb) [101][Ln4W4(Se2W14)2]2Fig. 13(j)3
[Yb4Se6W45O159(OH)6(H2O)11]18− [107]{Se2W13[Yb2W2(Se2W14)]2}Fig. 14(a)3
[(α-SeW9O33)2−{Ce2(CH3COO)(H2O)3W3O6}(α-Se2W14O52)]17− [108][Ce2W3(Se2W14)(SeW9)2]Fig. 14(b)3
[(α-SeW9O33)2−{Ce2(H2O)4W3O6}{α-Se2W14O51(OH)}]15− [108][Ce2W3(Se2W14)(SeW9)2]Fig. 14(c)3

Details of the “3d–4f clusters” involved in the manuscript

LnOCsLogogramIconSynthetic methodsa
a 1 stands for “lacunary POMs ligand-directed method”, 2 stands for “in-situ transformation lacunary POMs ligand directed method”, and 3 stands for “in-situ generation lacunary POMs ligand-directed method”, 4 stands for mixing multiple synthesis strategies.
[α-P2W16O57(OH)2CeIVMnIV6O9(O2CCH3)8]8− [119][CeMn6(P2W16)]Fig. 15(a)2
{[(α-P2W15O56)2Ce3Mn2(μ3-O)4(μ2-OH)2]3(μ2-OH)2(H2O)2(PO4)}47− [120][Ce3Mn2(P2W15O56)2]3Fig. 15(b)1
{[CeFe(AsW10O38)(H2O)2]3}15− [121][CeFe(AsW10)3]Fig. 163
[K9Ln6Fe6(H2O)12(SiW10O38)6]26− (Ln = Dy, Tb) [123][LnFe(SiW10)3]—2
[K9Sm6Fe6(H2O)12(GeW10O38)6]26− [124][SmFe(GeW10)3]—2
[K9Ln6Cr6(H2O)12(GeW10O38)6]26− (Ln = Dy, Tb) [122][LnCr(GeW10)3]—2
[{(GeW9O34)2Ln3(H2O)(OH)3}6{M2Ln3(μ3-OH)6(OH2)6}4]50− (Ln = Eu, Gd, Dy, Y; M = Zn, Mn, Co) [125–127][Ln30W8(GeW9)12]Fig. 17(a)1
[{CeIV(OAc)}CuII3(H2O)(B-α-GeW9O34)2]11− [128][CeCu3(GeW9)2]Fig. 17(d)1
{[Cu(en)2(H2O)][(Cu(en)(OH))3Ln(SiW11O39)(H2O)]}2 (Ln = Gd, Eu; en = ethylenediamine) [129][LnCu3(SiW11)2]Fig. 18(a)4
{[Cu(en)2(H2O)][Cu3Ln(en)3(OH)3(H2O)2(GeW11O39)]}2 (Ln = Eu, Tb, Dy) [130][LnCu3(GeW11)2]Fig. 18(b)4
{[Cu(dap)(H2O)3][LnCu3(dap)3(OH)3(H2O)(GeW11O39)]}2 (Ln = Sm, Eu, Gd, Tb; dap = 1,2-diaminopropane) [131][LnCu3(GeW11)2]Fig. 18(c)4
{[Cu(en)2(H2O)][DyCu3(en)3(OH)3(H2O)2(GeW11O39)]}2 [132][DyCu3(GeW11)2]Fig. 18(d)4
[LaNi12W35Sb3P3O139(OH)6]23− [134][LaNi12(PW9)3]Fig. 20(b)2
[La10Ni48W140Sb16P12O568(OH)24(H2O)20]86− [134][La10Ni48(PW9)12]Fig. 20(c)2
{[Fe(C6H16N2)Dy(H2O)2Fe2(B-α-GeW9O34)(GeW7O29)]2}20− [135][Fe2Dy(GeW9)(GeW7)]2Fig. 21(a)4
{[Dy(phen)Fe(B-α-GeW9O34)]2}8− (phen = 1,10-phenanthroline) [135][Fe2Dy2(GeW9)2]Fig. 21(b)4
{[LnNi3(OH)3(B-α-SiW9O34)]4B22O42}34− (Ln = Sm, Gd, Tb) [136][LnNi3(SiW9)]4Fig. 221
[{LnMnIII4(μ3-O)2(μ2-OH)2(H2O)(CO3)}(β-SiW8O31)2]13− (Ln = Ho, Tm, Yb) [138][LnMn4(SiW8)2]Fig. 23(a)2
[Ln{Zn2PW10O38(H2O)2}2]11− (Ln = Nd, Sm-Lu) [141][LnZn2(PW10)2]Fig. 23(b)2
{[Ln(H2O)8]2H2[Fe4(H2O)4(pic)4Ge2W20O72]} (Ln = La, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm; Hpic= picolinic acid) [142][Ln2Fe4(GeW10)2]—4
{[Ln(H2O)8]2[Fe4(H2O)8(L-thr)2(B-β-AsW9O33)2]} (Ln= La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er; L-thr = L-threonine) [140][Ln2Fe4(AsW9)2]—4
{[Gd(H2O)8]4[M(H2O)5]2[M4(H2O)2P4W30O112]} (M = MnII and CoII) [146][Gd4Co6(P2W15)2]—1
[FeM4{Ln(L)2}2O2(A-α-SiW9O34)2] (M = Mn, Cu; Ln = Gd, Dy, Lu; L = acetylacetonate (acac)) [145][FeM4L2(SiW9)2]Fig. 23(c)1
[FeMn4{Lu(L)2A}2O2(A-α-SiW9O34)2] (A = Ag, Na, K) [144][FeMn4Lu2A2(SiW9)2]Fig. 23(d)1
[Fe2Ln2(H2O)4(B-α-FeW9O34)2]10− (Ln = Dy, Ho, Y) [143][Fe2Ln2(FeW9)2]Fig. 20(a)2
[Ln(H2O)8]2[Fe4(H2O)8(thr)2][B-β-SbW9O33]2·22H2O (Ln = Pr, Nd, Sm, Eu, Gd, Dy, Lu; thr = threonine) [147][Fe4Ln2(SbW9)2]Fig. 20(d)4
[Ln3(H2O)5MII(H2O)3(Sb4O4)(SbW9O33)3(MIIW6O24)(WO2)3(CH3COO)]17− (Ln = La–Gd, M = Co; Ln = La, Pr, Nd, M = Ni; Ln = Ce, M = Zn) [133, 150][Ln3M2(SbW9)3]Fig. 19(b)1
[Ln3(H2O)3Ni3(H2O)6(SbW9O33)3(WO4)(CO3)]16− (Ln = La, Pr, Nd) [133][Ln3Ni3(SbW9)3]Fig. 19(a)4
[Ln3Ni9(μ3-OH)9(SbW9O33)2(PW9O34)3(CH3COO)3]30− (Ln = Dy, Er) [133][Ln3Ni9(PW9)3(SbW9)2]Fig. 19(c)2
[M(H2O)Ln3(H2O)5(W3O11)(SbW9O33)3]20− (M = Co, Ni; Ln= Tb, Dy, Ho, Er, Y) [148][Ln3Ni(SbW9)3]—2
[(HPz)11K4Fe6Ln(μ3-O)2(B-α-GeW9O34)2(GeW6O26)] (Pz = piperazine, Ln = Tb, Dy, Ho, Er) [151][LnFe6(GeW9)(GeW6)]—2
[Eu16Co7Se16W128O448(CIT)10(HCIT)2(NO3)4(OH)4(H2O)52]52− (H4CIT= citric acid) [152][Eu16Co7(Se2W14)8]Fig. 244

Comparison of Ueff values for POMs-based LnOCs

LnOCsUeff/kBDC field (Oe)
[ErW10O36]9− [163]55.2 KZero
[{Dy(H2O)2(α2-As2W17O61)}2]14− [54]11.8 K1000
[Dy4As5W40O144(H2O)10(Gly)2]21− [90]3.9 K10
[Dy(C4H2O6)(α-PW11O39)]216− [58]20 K4000
[FeMn4{Lu(L)2}2O2(A-α-SiW9O34)2] [144]19.7 KZero
[FeM4{Lu(L)2Ag}2O2(A-α-SiW9O34)2] [144]40.0 KZero
[FeM4{Lu(L)2Na}2O2(A-α-SiW9O34)2] [144]40.3 KZero
[FeM4{Lu(L)2K}2O2(A-α-SiW9O34)2] [144]26.7 KZero
[{(AsW9O33)Dy(H2O)2}6]36− [83]68 K3000
[{(AsW9O33)3Dy2(H2O)4W4O9(H2O)}2 (NH2(CH2PO3)2)]33− [87]101 KZero
[{(AsW9O33)3Dy2(H2O)4W4O9(H2O)}2 (NH2(CH2PO3)2)]33− [87]158 K5000
{[Dy(H2O)(Hpic)3][Dy(Hpic)2 (α2-P2W17O61)]}4− [60]119.38 K4000
[Dy9(CO3)3(ampH)2(H2O)12(PW10O37)6]35− [79]56 KZero
[(PW11O39)2Dy(OH)2(H2O)2]10− [55]98 cm−1Zero
[(PW11O39)2Dy2(F)2 (H2O)2]10− [55]74 cm−1Zero
[Gd{Zn2PW10O38(H2O)2}2]11− [141]6.30 K1000
[Tb{Zn2PW10O38(H2O)2}2]11− [141]4.54 K1000
[Er{Zn2PW10O38(H2O)2}2]11− [141]9.08 K1000
[Yb{Zn2PW10O38(H2O)2}2]11− [141]10.7 K1000
[Dy(α-PW11O39)2]11− [93]55 K3000
[{Dy(α-PW11O39)(H2O)3}2]8− [93]57 K3000
[(DyOH2)3(CO3)(α-PW9O34)2]11− [93]37 K3000
[Dy8(PW10O38)4(OH)4(H2O)2(W3O14)]26− [93]64 K3000
[Er(β2-GeW11O39)(α-GeW11O39)]13− [50]43.3 cm−1500
[Co(H2O)Dy3(H2O)5(W3O11)(SbW9O33)3]20− [150]9.0 K2500
[Ni(H2O)Dy3(H2O)5(W3O11)(SbW9O33)3]20− [150]6.5 K2000
[Fe2Dy2(H2O)4(B-α-FeW9O34)2]10− [143]50.24 KZero
[Fe2Dy2(H2O)4(B-α-FeW9O34)2]10− [143]80.21 K2500

Comparison of the proton conductivity in some representative POM-based LnOCsa

Compoundsσ (S·cm−1) (°C, RH)Ea (eV)
a σ: proton conductivity, Ea: proton transport activation energy, and RH: relative humidity.
[La10Ni48W140Sb16P12O568(OH)24(H2O)20]86− [134]2.05 × 10−2 (22 °C, 100%)3.74 × 10−3 (22 °C, 88%)6.86 × 10−4 (22 °C, 72%)3.28 × 10−4 (22 °C, 65%)3.09 × 10−4 (22 °C, 58%)3.25 × 10−4 (25 °C, 58%)3.57 × 10−4 (30 °C, 58%)3.92 × 10−4 (35 °C, 58%)4.45 × 10−4 (40 °C, 58%)4.89 × 10−4 (45 °C, 58%)0.22/58%
[La27Ge10W106O406(OH)4(H2O)24]59− [96]1.5 × 10−2 (85 °C, 98%)1.8 × 10−3 (30 °C, 98%)3.8× 10−4 (30 °C, 55%)1.5 × 10−2 (85 °C, 98%)0.42/98%
{[CeIV7CeIII3O6(OH)6(CO3)(H2O)11][(P2W16O59)]3}19− [80]2.65 × 10−4 (100 °C, 98%)1.95 × 10−7 (30 °C, 98%)0.36/98%
{[W14CeIV6O61]([W3Bi6CeIII3(H2O)3O14][B-α-BiW9O33]3)2}34− [165]2.4 × 10−3 (25 °C, 90%)2.6 × 10−4 (25 °C, 50%)4.9 × 10−7 (−40 °C)0.677/— Anhydrous
[Sc4(C2O4)4(B-β-SbW9O33)2][Sc4(H2O)2(C2O4)4(B-β-SbW9O33)2]28− [74]3.1× 10−2 (75 °C, 98%)7.9× 10−4 (25 °C, 98%)3.0× 10−4 (25 °C, 55%)0.28/98%
{[Gd2(H2O)11]2[Gd3(H2O)3(α-SiW11O39)2]2}2− [97]3.54 × 10−3 (85 °C, 98%)1.56 × 10−4 (25 °C, 98%)0.38/98%
{La10(μ3-OH)2(H2O)10[α(1,8)-GeW10O38]2[β(4,11)-GeW10O38]2}20− [82]6.35 × 10−4 (85 °C, 98%)4.68 × 10−5 (30 °C, 98%)8.66 × 10−7 (30 °C, 55%)0.49/98%