Graphical Abstract
View original image
Download original image
Show Outline
Figures (3)
Tables (1)
Table 1
Research Article | Open Access
Synthesis, structure, and characteristics of a hexa-Ti-oxo-cluster-added Keggin-type polyoxometalate
Abstract
An acentric hexa-Ti-oxo-cluster-added trimeric phosphotungstate, [H2N(CH3)2]3H12[Ti6O6(A-α-1,2-PW10O37)3]∙12 H2O (1), was synthesized by reacting trivacant polyoxometalate (POM) fragments with Ti4+ ions under hydrothermal conditions and characterized via single-crystal/powder X-ray diffraction, solid UV–vis and IR spectroscopies, and thermogravimetric analysis. The polyoxoanion of 1 is constituted by three Ti2O3(A-α-1,2-PW10O37) subunits linked through Ti–O–Ti bonds, forming a ring-shaped configuration. Furthermore, 1 exhibits a second-harmonic generation response about 0.6 times that of KH2PO4, which paves the way toward the development of Ti-added POMs in the field of nonlinear optical materials.
Electronic Supplementary Material
Download File(s)
0033_ESM1.pdf (755.4 KB)
0033_ESM2_y1.cif (1.9 MB)
References
[1]
Zhang, P. Y.; Wang, Y.; Yao, L. Y.; Yang, G. Y. Hepta-Zr-incorporated polyoxometalate assembly. Inorg. Chem. 2022, 61, 10410–10416.
[2]
Zhu, Z. K.; Lin, Y. Y.; Yu, H.; Li, X. X.; Zheng, S. T. Inorganic-organic hybrid polyoxoniobates: Polyoxoniobate metal complex cage and cage framework. Angew. Chem., Int. Ed. 2019, 58, 16864–16868.
[3]
Liu, J. C.; Zhao, J. W.; Streb, C.; Song, Y. F. Recent advances on high-nuclear polyoxometalate clusters. Coord. Chem. Rev. 2022, 471, 214734.
[4]
Wang, Z. W.; Yang, G. Y. A {Co9}-added polyoxometalate for efficient visible-light-driven hydrogen evolution. Molecules 2023, 28, 664.
[5]
Zhang, H. Y.; Zhao, W. L.; Li, H. Q.; Zhuang, Q. H.; Sun, Z. Q.; Cui, D. Y.; Chen, X. J.; Guo, A.; Ji, X.; An, S. et al. Latest progress in covalently modified polyoxometalates-based molecular assemblies and advanced materials. Polyoxometalates 2022, 1, 9140011.
[6]
Liu, J. X.; Zhang, X. B.; Li, Y. L.; Huang, S. L.; Yang, G. Y. Polyoxometalate functionalized architectures. Coord. Chem. Rev. 2020, 414, 213260.
[7]
Li, J.; Zhang, D.; Chi, Y. N.; Hu, C. W. Catalytic application of polyoxovanadates in the selective oxidation of organic molecules. Polyoxometalates 2022, 1, 9140012.
[8]
Zang, D. J.; Wang, H. Q. Polyoxometalate-based nanostructures for electrocatalytic and photocatalytic CO2 reduction. Polyoxometalates 2022, 1, 9140006.
[9]
Li, H. L.; Lian, C.; Yang, G. Y. A Zr-added Dawson-type poly(polyoxometalate). Dalton Trans. 2023, 52, 857–861.
[10]
Lian, C.; Li, H. L.; Yang, G. Y. A new 28-Ni-added poly(polyoxometalate) with B atoms: Synthesis, structure and catalysis for Knoevenagel condensation. Sci. China Chem. 2023, 66, 1394–1399.
[11]
Li, H. L.; Lian, C.; Yang, G. Y. A new 4-Ti-added polyoxometalate. Tungsten, in press, DOI: 10.1007/s42864-023-00221-5.
[12]
Li, H. L.; Lian, C.; Yang, G. Y. {Ti12} cluster-added poly(polyoxometalate) containing mixed trivacant Keggin and Dawson fragments. Inorg. Chem. 2023, 62, 9014–9018.
[13]
Chakraborty, B.; Weinstock, I. A. Water-soluble titanium-oxides: Complexes, clusters and nanocrystals. Coord. Chem. Rev. 2019, 382, 85–102.
[14]
Ni, Z. H.; Lv, H. J.; Yang, G. Y. Recent advances of Ti/Zr-substituted polyoxometalates: From structural diversity to functional applications. Molecules 2022, 27, 8799.
[15]
Nomiya, K.; Sakai, Y.; Matsunaga, S. Chemistry of group IV metal ion‐containing polyoxometalates. Eur. J. Inorg. Chem. 2011, 2011, 179–196.
[16]
Li, H. L.; Lian, C.; Yang, G. Y. A ring-shaped 12-Ti-substituted poly(polyoxometalate): Synthesis, structure, and catalytic properties. Sci. China Chem. 2022, 65, 892–897.
[17]
Kortz, U.; Hamzeh, S. S.; Nasser, N. A. Supramolecular structures of titanium(IV)-substituted Wells-Dawson polyoxotungstates. Chem.—Eur. J. 2003, 9, 2945–2952.
[18]
Sakai, Y.; Yoza, K.; Kato, C. N.; Nomiya, K. Tetrameric, trititanium(IV)-substituted polyoxotungstates with an α-Dawson substructure as soluble metal-oxide analogues: Molecular structure of the Giant “tetrapod” [( α-1,2,3-P2W15Ti3O62)4{ μ3-Ti(OH)3}4Cl]45−. Chem.—Eur. J. 2003, 9, 4077–4083.
[19]
Hussain, F.; Bassil, B. S.; Bi, L. H.; Reicke, M.; Kortz, U. Structural control on the nanomolecular scale: Self-assembly of the polyoxotungstate wheel [{ β-Ti2SiW10O39}4]24−. Angew. Chem., Int. Ed. 2004, 43, 3485–3488.
[20]
Li, H. L.; Lian, C.; Yin, D. P.; Jia, Z. Y.; Yang, G. Y. A new hepta-nuclear Ti-oxo-cluster-substituted tungstoantimonate and its catalytic oxidation of thioethers. Cryst. Growth Des. 2019, 19, 376–380.
[21]
Kholdeeva, O. A.; Maksimov, G. M.; Maksimovskaya, R. I.; Kovaleva, L. A.; Fedotov, M. A.; Grigoriev, V. A.; Hill, C. L. A dimeric titanium-containing polyoxometalate. Synthesis, characterization, and catalysis of H2O2-based thioether oxidation. Inorg. Chem. 2000, 39, 3828–3837.
[22]
Hideyuki, M.; Kunihiko, H.; Ikuo, T.; Takeshi, H.; Shoko, Y.; Rie, M.; Nozaki, K. C.; Kenji, N. Novel solid-state 8H+-heteropolyacid. Synthesis and molecular structure of a free-acid form of a Dawson-type sandwich complex, [Ti2{P2W15O54(OH2)2}2]8−. Bull. Chem. Soc. Jpn. 2007, 80, 2161–2169.
[23]
He, J. H.; Wang, X. H.; Chen, Y. G.; Liu, J. F.; Hu, N. H.; Jia, H. Q. Synthesis and crystal structure of the dimeric, Ti-O-Ti bridged hydrid form polyoxoanion [ α-1,2-PW10Ti2O39]210−. Inorg. Chem. Commun. 2002, 5, 796–799.
[24]
Lin, Y.; Weakley, T. J. R.; Rapko, B.; Finke, R. G. Polyoxoanions derived from tungstosilicate A- β-SiW9O3410−: Synthesis, single-crystal structural determination, and solution structural characterization by tungsten-183 NMR and IR of titanotungstosilicate A- β-Si2W18Ti6O7714−. Inorg. Chem. 2002, 32, 5095–5101.
[25]
Matsuki, Y.; Hoshino, T.; Takaku, S.; Matsunaga, S.; Nomiya, K. Synthesis and molecular structure of a water-soluble, dimeric tri-titanium(IV)-substituted Wells-Dawson polyoxometalate containing two bridging (C5Me5)Rh2+ groups. Inorg. Chem. 2015, 54, 11105–11113.
[26]
Al-Kadamany, G.; Bassil, B. S.; Raad, F.; Kortz, U. The oxalato-titanium-containing tungstophosphate(V) dimers, [Ti8(C2O4)8P2W18O76(H2O)4]18− and [Ti6(C2O4)4P4W32O124]20−. J. Clust. Sci. 2014, 25, 867–878.
[27]
Hoshino, T.; Isobe, R.; Kaneko, T.; Matsuki, Y.; Nomiya, K. Synthesis and molecular structure of a novel compound containing a carbonate-bridged hexacalcium cluster cation assembled on a trimeric trititanium (IV)-substituted Wells-Dawson polyoxometalate. Inorg. Chem. 2017, 56, 9585–9593.
[28]
Nsouli, N. H.; Bassil, B. S.; Dickman, M. H.; Kortz, U.; Keita, B.; Nadjo, L. Synthesis and structure of dilacunary decatungstogermanate, [ γ-GeW10O36]8−. Inorg. Chem. 2006, 10, 3858–3860.
[29]
Ren, Y. H.; Liu, S. X.; Cao, R. G.; Zhao, X. Y.; Cao, J. F.; Gao, C. Y. Two trimeric tri-TiIV-substituted Keggin tungstogermanates based on tetrahedral linkers. Inorg. Chem. Commun. 2008, 11, 1320–1322.
[30]
Li, H. L.; Lian, C.; Yang, G. Y. A {Ti6W4}-cluster-substituted polyoxotungstate: Synthesis, structure, and catalytic oxidation properties. Inorg. Chem. 2021, 60, 14622–14628.
[31]
Li, H. L.; Lian, C.; Yang, G. Y. {Ti6}/{Ti10} wheel cluster substituted silicotungstate aggregates. Inorg. Chem. 2021, 60, 16852–16859.
[32]
Hervé, G.; Teze, A. Study of α- and β-enneatungstosilicates and -germanates. Inorg. Chem. 1976, 16, 2115–2117.
[33]
Sheldrick, G. M. SHELXT—Integrated space-group and crystal-structure determination. Acta Crystallogr. Sect. A Found. Adv. 2015, 71, 3–8.
[34]
Sheldrick, G. M. A short history of SHELX. Acta Crystallogr. Sect. A: Found. Crystallogr. 2008, 64, 112–122.
[35]
Kurtz, S. K.; Perry, T. T. A powder technique for the evaluation of nonlinear optical materials. J. Appl. Phys. 1968, 8, 3798–3813.
[36]
Zhang, G. Y.; Hou, J.; Li, M. Z.; Tung, C. H.; Wang, Y. F. Counteranion-stabilized titanium(IV) isopolyoxocationic clusters isolated from water. Inorg. Chem. 2016, 55, 4704–4709.
[37]
Kemmitt, T.; Al-Salim, N. I.; Gainsford, G. J. Formation and structural characterisation of an unusual cyclic hexameric oxotitanium complex. 3.0.CO;2-I">Eur. J. Inorg. Chem. 1999, 1999, 1847–1849.
[38]
Baumann, S. O.; Bendova, M.; Fric, H.; Puchberger, M.; Visinescu, C.; Schubert, U. Ketoximate derivatives of titanium alkoxides and partial hydrolysis products thereof. Eur. J. Inorg. Chem. 2009, 2009, 3333–3340.
[39]
Gao, M. Y.; Chen, S. M.; Hu, L. X.; Zhang, L.; Zhang, J. Synthesis and photocatalytic H2 evolution properties of four titanium-oxo-clusters based on a cyclohex-3-ene-1-carboxylate ligand. Dalton Trans. 2017, 46, 10630–10634.
[40]
Narayanam, N.; Fang, W. H.; Chintakrinda, K.; Zhang, L.; Zhang, J. Deep eutectic-solvothermal synthesis of titanium-oxo clusters protected by π-conjugated chromophores. Chem. Commun. 2017, 53, 8078–8080.
[41]
Lian, C.; Li, H. L.; Yang, G. Y. High-nuclear Ni-substituted poly(polyoxometalate) containing an Anderson-like {Cs7} cluster. Inorg. Chem. 2022, 61, 11335–11341.
[42]
Wendlandt, W. W.; Hecht, H. G. Reflectance Spectroscopy; Interscience Publishers: New York, 1966.
[43]
Wei, Q.; Sun, L.; Zhang. J.; Yang, G. Y. Two deep-ultraviolet nonlinear optical alkaline-earth metal borates based on different types of oxoboron clusters. Dalton Trans. 2017, 46, 7911–7916.
[44]
Knoppe, S.; Häkkinen, H.; Verbiest, T.; Clays, K. Role of donor and acceptor substituents on the nonlinear optical properties of gold nanoclusters. J. Phys. Chem. C 2018, 122, 4019–4028.
[45]
Lacroix, P. G.; Malfant, I.; Lepetit, C. Second-order nonlinear optics in coordination chemistry: An open door towards multi-functional materials and molecular switches. Coord. Chem. Rev. 2016, 308, 381–394.
[46]
Li, X. Y.; Li, J. H.; Cheng, J. W.; Yang, G. Y. Two acentric aluminoborates incorporated d10 cations: Syntheses, structures, and nonlinear optical properties. Inorg. Chem. 2023, 36, 1264–1271.
[47]
Guan, W.; Yang, G. C.; Yan, L. K.; Su, Z. M. Prediction of second-order optical nonlinearity of trisorganotin-substituted β-Keggin Polyoxotungstate. Inorg. Chem. 2006, 45, 7864–7868.
[48]
Ma, T. Y.; Zhang, T.; Zhu, B.; Yan, L. K.; Su, Z. M. Theoretical studies on oxidation-switchable second-order nonlinear optical responses of Metallosalen-Keggin polyoxometalate derivatives. RSC Adv. 2016, 6, 53438–53443.
[49]
Luo, X. M.; Chen, L.; Dong, Y. Y.; Li, J.; Cui, C. H.; Cao, J. P.; Xu, Y. Three new high-nuclear transition-metal-substituted heteropolytungstates: Syntheses, crystal structures, magnetic studies and NLO properties. Dalton Trans. 2018, 47, 9504–9511.
[50]
Wang, Z. W.; Zhao, Q.; Chen, C. A.; Sun, J. J.; Lv, H. J.; Yang, G. Y. Chiral {Ni6PW9} cluster-organic framework: Synthesis, structure, and properties. Inorg. Chem. 2022, 61, 7477–7483.
[51]
Li, F. J.; Hu, X. J.; Sa, R. J.; Niu, L. B. Molecular orbital closed loops analysis of the third-order NLO response of polyanion [M8O26]4− (M = Cr, Mo, W): A TDDFT study. Struct. Chem. 2014, 25, 539–549.
[52]
Bai, Z. Y.; Hu, C. L.; Liu, L. H.; Zhang, L. Z.; Huang, Y. S.; Yuan, F. F.; Lin, Z. B. KMg(H2O)PO4: A deep-ultraviolet transparent nonlinear optical material derived from KTiOPO4. Chem. Mater. 2019, 31, 9540–9545.
[53]
Lei, B. H.; Yang, Z. H.; Yu, H. W.; Cao, C.; Li, Z.; Hu, C.; Poeppelmeier, K. R.; Pan, S. L. Module-guided design scheme for deep-ultraviolet nonlinear optical materials. J. Am. Chem. Soc. 2018, 140, 10726–10733.
Pages 9140033-9140033
Cite this article:
Wang Y, Li H-L, Yang G-Y. Synthesis, structure, and characteristics of a hexa-Ti-oxo-cluster-added Keggin-type polyoxometalate. Polyoxometalates, 2023, 2(3): 9140033. https://doi.org/10.26599/POM.2023.9140033
Metrics & Citations
Article History
Copyright
Rights and Permissions
京公网安备11010802044758号