Citation: Zhengzheng LIU, Pengyun ZHANG, Chengri WANG, Shengli HUANG, Guoyu YANG. Synthesis, structure, and electrochemical properties of a sandwich-type {Co₆}-cluster-added germanotungstate[J]. Chinese Journal of Inorganic Chemistry, ;2024, 40(6): 1173-1179. doi: 10.11862/CJIC.20240039 shu

Synthesis, structure, and electrochemical properties of a sandwich-type {Co₆}-cluster-added germanotungstate

MOE Key Laboratory of Cluster Science, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488, China

Corresponding author: Shengli HUANG, huangsl@bit.edu.cn Guoyu YANG, ygy@bit.edu.cn
Received Date: 27 January 2024
Revised Date: 25 March 2024

Figures(8)

A new sandwich-type {Co₆}-added polyoxotungstate, [Co(dien)₂]{[Co(dien)(H₂O)]₂[Co(dien)]2[Co₆(en)₂(μ₃-OH)₂(H₂O)₆(GeW₈O₃₁)₂]}·5.5H₂O (1), where dien=diethylenetriamine and en=ethylenediamine, was synthesized via hydrothermal reaction. The polyoxoanion of compound 1 was constructed by a belt-like {Co₆} cluster core sandwiched by two {GeW₈} units. 1 was characterized by single crystal X-ray diffraction, element analysis, IR spectroscopy, powder X-ray diffraction (PXRD), and thermogravimetric analysis (TGA) experiments, respectively. The electrochemical properties of 1 were explored by the cyclic voltammetry (CV) technique, and 1 exhibited excellent electrocatalytic activity in nitrite reduction.
- polyoxometalate,
- co-added polyoxotungstate,
- sandwich-type structure,
- hydrothermal synthesis,
- reduction of nitrite
1. [1]
  Miras H N, Yan J, Long D, Cronin L. Engineering polyoxometalates with emergent properties[J]. Chem. Soc. Rev., 2012,41:7403-7430. doi: 10.1039/c2cs35190k
2. [2]
  Liu J X, Zhang X B, Li Y L, Huang S L, Yang G Y. Polyoxometalate functionalized architectures[J]. Coord. Chem. Rev., 2020,414:213-260.
3. [3]
  Zhang Q, Li F Y, Xu L. Application of polyoxometalates (POMs) in the third generation of solar cells[J]. Polyoxometalates, 2023,29140018. doi: 10.26599/POM.2022.9140018
4. [4]
  Zheng S T, Yang G Y. Recent advances in paramagnetic-TM-substituted polyoxometalates[J]. Chem. Soc. Rev., 2012,41:7623-7646. doi: 10.1039/c2cs35133a
5. [5]
  Wang S S, Yang G Y. Recent advances in polyoxometalate-catalyzed reactions[J]. Chem. Rev., 2015,115:4893-4962. doi: 10.1021/cr500390v
6. [6]
  YANG Guoyu. OXO cluster chemistry. Beijing: Science Press, 2012: 224-261
7. [7]
  CHEN Weilin, WANG Enbo. Polyoxometalate chemistry. Beijing: Science Press, 2013: 45-84
8. [8]
  Li H L, Lian C, Yang G Y. A Zr-added Dawson-type poly(polyoxometalate)[J]. Dalton Trans., 2023,52:857-861. doi: 10.1039/D2DT03820J
9. [9]
  Weakley T J R, Evans H T, Showell J S. 18-Tungstotetracobalto(Ⅱ) diphosphate and related anions: A novel structural class of heteropolyanions[J]. J. Chem. Soc. Chem. Commun., 1973:139-140.
10. [10]
  Francis B, Leyrie M, Herve G. Structure of potassium diaquatricuprooctadecatungstodiarsenate􀃮(12-) undecahydrate[J]. Acta Crystallogr. Sect. B, 1982,B38:358-362.
11. [11]
  Limanski E M, Drewes D, Droste E, Bohner R, Kerbs B. Syntheses and X-ray characterization of novel tellurium-substituted lacunary polyoxotungstates containing V^Ⅳ, Co^Ⅱ, Ni^Ⅱ and Zn^Ⅱ as heteroatoms[J]. J. Mol. Struct., 2003,656:17-25. doi: 10.1016/S0022-2860(03)00340-5
12. [12]
  Knoth W H, Domaille P J, Farlee R D. Anions of the type (RMOH₂)₃ W₁₈P₂O₆₈^9- and[H₂OCo]₃W₁₈P₂O₆₈^12-. A reinvestigation of "B, β-W₉PO₃^49-"[J]. Organometallics, 1985,4:62-68. doi: 10.1021/om00120a012
13. [13]
  Zhao J W, Li B, Zheng S T, Yang G Y. Two-dimensional extended (4, 4)-topological network constructed from tetra-Ni^Ⅱ-substituted sandwich-type Keggin polyoxometalate building blocks and Ni^Ⅱ-organic cation bridges[J]. Cryst. Growth Des., 2007,7:3130-3133.
14. [14]
  Kikukawa Y, Suzuki K, Yamaguchi K, Mizuno N. Synthesis, structure characterization, and reversible transformation of a cobalt salt of a dilacunary γ-Keggin silicotungstate and sandwich-type di- and tetracobalt-containing silicotungstate dimers[J]. Inorg. Chem., 2013,52:8644-8652. doi: 10.1021/ic4008075
15. [15]
  Xue H, Zhang Z, Yang B F, Liu H S, Yang G Y. Hydrothermal syntheses and structures of two tetra-Co^Ⅱ substituted sandwiched polyoxometalates[J]. J. Clust. Sci., 2016,27:1439-1449. doi: 10.1007/s10876-016-1010-2
16. [16]
  Guo L Y, Zeng S Y, Jaglicic Z, Hu Q D, Wang S X, Wang Z, Sun D. A pyridazine-bridged sandwiched cluster incorporating planar hexanuclear cobalt ring and bivacant phosphotungstate[J]. Inorg. Chem., 2016,55:9006-9011. doi: 10.1021/acs.inorgchem.6b01468
17. [17]
  Chen W C, Wang X L, Qin C, Shao K Z, Su Z M, Wang E B. A carbon-free polyoxometalate molecular catalyst with a cobalt-arsenic core for visible light-driven water oxidation[J]. Chem. Commun., 2016,52:9514-9517. doi: 10.1039/C6CC03763A
18. [18]
  Zhang Z, Sun K N, Yang G Y. Two series of Cu^Ⅱ-substituted sandwich-type polyoxotungstates constructed from trivacant germanotungstate fragments[J]. ChemistrySelect, 2019,4:7559-7565. doi: 10.1002/slct.201901273
19. [19]
  Ginsberg P. Inorganic Syntheses. New York: Wiley, 1990.
20. [20]
  Sheldrick G M. Crystal structure refinement with SHELXL[J]. Acta Crystallogr. Sect. C, 2015,C71:3-8.
21. [21]
  Dolomanov O V, Bourhis L J, Gildea R J, Howard J A K, Puschmann H. OLEX2: A complete structure solution, refinement and analysis program[J]. J. Appl. Crystallogr., 2009,42:339-341. doi: 10.1107/S0021889808042726
22. [22]
  Rees B, Jenner L, Yusupov M. Bulk-solvent correction in large macromolecular structures[J]. Acta Crystallogr. Sect. D, 2005,D61:1299-1301.
23. [23]
  Mikysek T, Švancara I, Kalcher K, Bartoš M, Vytřas K, Ludvík J. New approaches to the characterization of carbon paste electrodes using the ohmic resistance effect and qualitative carbon paste indexes[J]. Anal. Chem., 2009,81:6327-6333. doi: 10.1021/ac9004937
24. [24]
  Zhang Z M, Qin Y F, Qin C, Li Y G, Wang E B, Wang X L, Su Z M, Xu L. Two multi-copper-containing heteropolyoxotungstates constructed from the lacunary Keggin polyoxoanion and the high-nuclear spin cluster[J]. Inorg. Chem., 2007,46:8162-8169. doi: 10.1021/ic7012864
25. [25]
  Ibrahim M, Xiang Y X, Bassil B S, Lan Y H, Powell A K, De Oliveira P, Keita B, Kortz U. Synthesis, magnetism, and electrochemistry of the Ni₁₄- and Ni₅-containing heteropolytungstates[Ni₁₄(OH)₆(H₂O)₁₀(HPO₄)₄(P₂W₁₅O₅₆)₄]^34- and[Ni₅(OH)₄(H₂O)₄(β-GeW₉O₃₄)(β-GeW₈O₃₀(OH))]^13-[J]. Inorg. Chem., 2013,52:8399-8408. doi: 10.1021/ic400943j
26. [26]
  Nsouli N H, Ismail A H, Helgadottir I S, Dickman M H, Clement-Juan J M, Kortz U. Copper-, cobalt-, and manganese-containing 17-tungsto-2-germanates[J]. Inorg. Chem., 2009,48:5884-5890. doi: 10.1021/ic900180x
27. [27]
  Wang C M, Zheng S T, Yang G Y. Novel copper-complex-substituted tungstogermanates[J]. Inorg. Chem., 2007,46:616-618. doi: 10.1021/ic0618605
28. [28]
  Huang L, Wang S S, Zhao J W, Cheng L, Yang G Y. Synergistic combination of multi-Zr^Ⅳ cations and lacunary Keggin germanotungstates leading to a gigantic Zr₂₄-cluster-substituted polyoxometalate[J]. J. Am. Chem. Soc., 2014,136:7637-7642. doi: 10.1021/ja413134w
29. [29]
  Sun J J, Wang Y L, Yang G Y. Two new hexa-Ni-substituted polyoxometalates in the form of an isolated cluster and 1-D chain: Syntheses, structures, and properties[J]. CrystEngComm, 2020,22:8387-8393. doi: 10.1039/D0CE01446J
30. [30]
  Zhao J W, Zheng S T, Li Z H, Yang G Y. Combination of lacunary polyoxometalates and high-nuclear transition-metal clusters under hydrothermal conditions: First 6⁵·8 CdSO₄-type 3-D framework built by hexa-Cu^Ⅱ sandwiched polyoxotungstates[J]. Dalton Trans., 2009:1300-1306.
31. [31]
  Zhang L Z, Gu W, Liu X, Dong Z L, Yang Y S, Li B, Liao D Z. K₁₀[Co₄(H₂O)₂(B-α-SiW₉O₃₄H)₂]·21H₂O: A sandwich polyoxometalate based on the magnetically interesting element cobalt[J]. Inorg. Chem. Commun., 2007,10:1378-1380. doi: 10.1016/j.inoche.2007.08.025
32. [32]
  Brown I D, Altermatt D. Bond-valence parameters obtained from a systematic analysis of the inorganic crystal structure database[J]. Acta Crystallogr. Sect. B, 1985,B41:244-247.
33. [33]
  Wang J P, Ma P T, Shen Y, Niu J Y. Tetra-transition-metal substituted Weakley-type sandwich germanotungstates and their derivatives decorated by transition-metal complexes[J]. Cryst. Growth Des., 2008,8:3130-3133. doi: 10.1021/cg701278b
34. [34]
  Zhang Z M, Wang E B, Qi Y F, Li Y G, Mao B D, Su Z M. Synthesis, characterization, and crystal structures of double-cubane-substituted and asymmetric penta-Ni-substituted dimeric polyoxometalates[J]. Cryst. Growth Des., 2007,7:1305-1311. doi: 10.1021/cg060868m
35. [35]
  Wuhai University. Chemical analysis: Vol. Ⅱ. 6th ed. Beijing: Higher Education Press, 2018: 240-249
36. [36]
  Sun J J, Wang W D, Li X Y, Yang B F, Yang G Y. {Cu₈} cluster-sandwiched polyoxotungstates and their polymers: Syntheses, structures, and properties[J]. Inorg. Chem., 2021,60:10459-10647.
37. [37]
  Zhang Z, Sun K N, Yang G Y. Two series of Cu^Ⅱ-substituted sandwich-type polyoxotungstates constructed from trivacant germanotungstate fragments[J]. ChemistrySelect, 2019,4:7559-7565.
38. [38]
  Ibrahim M, Haider A, Xiang Y X, Bassil B S, Carey A M, Rullik L, Jameson G B, Doungmene F, Mbomekallé I M, De Oliveira P, Mereacre V, Kostakis G E, Powell A K, Kortz U. Tetradecanuclear iron􀃮-oxo nanoclusters stabilized by trilacunary heteropolyanions[J]. Inorg. Chem., 2015,54:6136-6146.
39. [39]
  Yang Z X, Liang X W, Lin D M, Zheng Q J, Huo Y. Heteroatom-modulated assembly of hexalanthanoid-containing polyoxometalate-based coordination networks[J]. Inorg. Chem., 2023,62:1466-1475.
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Synthesis, structure, and electrochemical properties of a sandwich-type {Co₆}-cluster-added germanotungstate