Citation: Lin GENG, Wei-Hui FANG, Lei ZHANG, Jian ZHANG. Gadolinium Pivalate Complex as a Precursor for the Synthesis of Titanium Oxo Clusters: Solvent Influence and Structural Analysis[J]. Chinese Journal of Structural Chemistry, ;2020, 39(6): 1063-1069. doi: 10.14102/j.cnki.0254-5861.2011-2551 shu

Gadolinium Pivalate Complex as a Precursor for the Synthesis of Titanium Oxo Clusters: Solvent Influence and Structural Analysis

Lin GENG ^{a, b} ,
Wei-Hui FANG ^b,, ,
Lei ZHANG ^b ,
Jian ZHANG ^b

a.
College of Chemistry and Materials Science, Fujian Normal University, Fuzhou 350007, China
b.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China

Corresponding author: Wei-Hui FANG, fwh@fjirsm.ac.cn
Received Date: 26 July 2019
Accepted Date: 15 October 2019

Fund Project: the National Natural Science Foundation of China 21771181the National Natural Science Foundation of China 21673238Youth Innovation Promotion Association CAS 2017345Shanghai Key Laboratory of Rare Earth Functional Materials and Natural Science Foundation of Fujian Province 2017J05036

Figures(5)

In this text, we present researches on the synthesis of polyoxo-titanium clusters (PTCs) by the use of gadolinium pivalate precursor. During the synthesis process, we discover that solvents play an important role. When acetonitrile was used as solvent, Ti₈Gd(μ₂-O)(μ₃-O)₅(Sal)₅(OPiv)₂(μ₂-OⁱPr)₃(μ-OⁱPr)₈ (PTC-82) (H₂Sal = salicylic acid, HOPiv = pivalic acid) was obtained. When N, N-dimethylformamide (DMF) was used as solvent under the same reaction conditions, Ti₄Gd₂(μ₃-O)₂(Sal)₄(OPiv)₄(μ₂-OⁱPr)₂(μ-OⁱPr)₄(DMF)₂ (PTC-83) was synthesized. The solid-state UV absorption spectra revealed that the dopant of lanthanide and the incorporation of salicylic acid ligands have successfully narrowed the bandgap of PTCs. In addition, they exhibited rapid and reproducible photo-responses.
- lanthanide pivalate,
- dopant,
- polyoxo-titanium clusters,
- bandgap,
- photocurrent
1. [1]
  Shen, S.; Chen, J.; Wang, M.; Sheng, X.; Chen, X.; Feng, X.; Mao, S. S. Titanium dioxide nanostructures for photoelectrochemical applications. Prog. Mater. Sci. 2018, 98, 299–385. doi: 10.1016/j.pmatsci.2018.07.006
2. [2]
  Zhang, H.; Ma, L.; Ming, J.; Liu, B.; Zhao, Y.; Hou, Y.; Ding, Z.; Xu, C.; Zhang, Z.; Long, J. Amorphous Ta₂O_xN_y-enwrapped TiO₂ rutile nanorods for enhanced solar photoelectrochemical water splitting. Appl. Catal. B-Environ. 2019, 243, 481–489. doi: 10.1016/j.apcatb.2018.10.024
3. [3]
  Chen, X.; Mao, S. S. Titanium dioxide nanomaterials: synthesis, properties, modifications, and applications. Chem. Rev. 2007, 107, 2891–2959. doi: 10.1021/cr0500535
4. [4]
  Liu, J. X.; Gao, M. Y.; Fang, W. H.; Zhang, L.; Zhang, J. Frontispiece: bandgap engineering of titanium-oxo clusters: labile surface sites used for ligand substitution and metal incorporation. Angew. Chem. Int. Ed. 2016, 55, 5160–5165. doi: 10.1002/anie.201510455
5. [5]
  Fang, W. H.; Wang, J. F.; Zhang, L.; Zhang, J. Titanium-oxo cluster based precise assembly for multidimensional materials. Chem. Mater. 2017, 29, 2681–2684. doi: 10.1021/acs.chemmater.7b00324
6. [6]
  Fang, W. H.; Zhang, L.; Zhang, J. Assembly of titanium-oxo cations with copper-halide anions to form supersalt-type cluster-based materials. Chem. Commun. 2017, 53, 3949–3951. doi: 10.1039/C7CC01443K
7. [7]
  Li, N.; Matthews, P. D.; Luo, H. K.; Wright, D. S. Novel properties and potential applications of functional ligand-modified polyoxotitanate cages. Chem. Commun. 2016, 52, 11180–11190. doi: 10.1039/C6CC03788G
8. [8]
  Matthews, P. D.; King, T. C.; Wright, D. S. Structure, photochemistry and applications of metal-doped polyoxotitanium alkoxide cages. Chem. Commun. 2014, 50, 12815–12823. doi: 10.1039/C4CC04421E
9. [9]
  Eslava, S.; Hengesbach, F.; McPartlin, M.; Wright, D. S. Heterometallic cobalt(ii)-titanium(iv) oxo cages; key building blocks for hybrid materials. Chem. Commun. 2010, 46, 4701–4703. doi: 10.1039/c0cc00016g
10. [10]
  Eslava, S.; Goodwill, B. P. R.; McPartlin, M. D.; Wright, D. Extending the family of titanium heterometallic-oxo-alkoxy cages. Inorg. Chem. 2011, 50, 5655–5662. doi: 10.1021/ic200350j
11. [11]
  Chen, Y.; Jarzembska, K. N.; Trzop, E.; Zhang, L.; Coppens, P. How does substitutional doping affect visible light absorption in a series of homodisperse Ti₁₁ polyoxotitanate nanoparticles? Chem. Eur. J. 2015, 21, 11538–11544. doi: 10.1002/chem.201500961
12. [12]
  Artner, C.; Koyun, A.; Czakler, M.; Schubert, U. Mixed-metal oxo clusters structurally derived from Ti₆O₄(OR)₈(OOCR′)₈. Eur. J. Inorg. Chem. 2014, 29, 5008–5014.
13. [13]
  Daniele, S.; Hubertpfalzgraf, L. G.; Daran, J. C.; Halut, S. Synthesis and molecular structure of [Sm₄Ti(μ₅-O)(μ₃-OR)₂(μ-OR)₆(OR)₆] (R = Prⁱ): a novel framework for heteronuclear alkoxides with a 1: 4 stoichiometry. Polyhedron 1994, 13, 927–932. doi: 10.1016/S0277-5387(00)83012-0
14. [14]
  Lv, Y.; Cai, Z.; Yan, D.; Su, C.; Li, W.; Chen, W.; Ren, Z.; Wei, Y.; Mi, O.; Zhang, C.; Wright, D. S. Novel Eu-containing titania composites derived from a new Eu(iii)-doped polyoxotitanate cage. RSC Adv. 2016, 6, 57–60. doi: 10.1039/C5RA22857C
15. [15]
  Artner, C.; Kronister, S.; Czakler, M.; Schubert, U. Ion-size-dependent formation of mixed titanium/lanthanide oxo clusters. Eur. J. Inorg. Chem. 2014, 2014, 5596–5602. doi: 10.1002/ejic.201402670
16. [16]
  Li, N.; Garcia-Rodriguez, R.; Matthews, P. D.; Luo, H. K.; Wright, D. S. Synthesis, structure and paramagnetic NMR analysis of a series of lanthanide-containing [LnTi₆O₃(OⁱPr)₉(salicylate)₆] cages. Dalton Trans. 2017, 46, 4287–4295. doi: 10.1039/C7DT00049A
17. [17]
  Lv, Y.; Willkomm, J.; Leskes, M.; Steiner, A.; King, T. C.; Gan, L.; Reisner, E.; Wood, P. T.; Wright, D. S. Formation of Ti₂₈Ln cages, the highest nuclearity polyoxotitanates (Ln = La, Ce). Chem. Eur. J. 2012, 18, 11867–11870. doi: 10.1002/chem.201201827
18. [18]
  Lv, Y.; Du, W.; Ren, Y.; Cai, Z.; Yu, K.; Zhang, C.; Chen, Z.; Wright, D. S. An integrated electrochromic supercapacitor based on nanostructured Er-containing titania using an Er(iii)-doped polyoxotitanate cage. Inorg. Chem. Front. 2016, 3, 1119–1123. doi: 10.1039/C6QI00114A
19. [19]
  Wang, S.; Su, H. C.; Yu, L.; Zhao, X. W.; Qian, L. W.; Zhu, Q. Y.; Dai, J. Fluorescence and energy transfer properties of heterometallic lanthanide-titanium oxo clusters coordinated with anthracenecarboxylate ligand. Dalton Trans. 2015, 44, 1882–1888. doi: 10.1039/C4DT02968B
20. [20]
  Zhang, G. L.; Wang, S.; Hou, J. L.; Mo, C. J.; Que, C. J.; Zhu, Q. Y.; Dai, J. A lanthanide-titanium (LnTi₁₁) oxo-cluster, a potential molecule based fluorescent labelling agent and photocatalyst. Dalton Trans. 2016, 45, 17681–17686. doi: 10.1039/C6DT03034C
21. [21]
  Lu, D. F.; Kong, X. J.; Lu, T. B.; Long, L. S.; Zheng, L. S. Heterometallic lanthanide-titanium oxo clusters: a new family of water oxidation catalysts. Inorg. Chem. 2017, 56, 1057–1060. doi: 10.1021/acs.inorgchem.6b03072
22. [22]
  Zheng, H.; Du, M. H.; Lin, S. C.; Tang, Z. C.; Kong, X. J.; Long, L. S.; Zheng, L. S. Assembly of a wheel-like Eu₂₄Ti₈ cluster under the guidance of high-resolution electrospray ionization mass spectrometry. Angew. Chem. Int. Ed. 2018, 57, 10976–10979. doi: 10.1002/anie.201806757
23. [23]
  Hubert-Pfalzgraf, L. G.; Abada, V.; Vaissermann, J. Formation of mixed-metal alkoxides mediated by the reactivity of coordinated pinacol: synthesis and molecular structures of Ce₂Ti₂(μ₃-O)₂(μ, η²-OCMe₂CMe₂O)₄(OPrⁱ)₄(PrⁱOH)₂ and of Ce₂Nb₂(μ₃-O)₂(μ, η²-OCMe₂CMe₂O)₄(OPrⁱ)₆. Polyhedron 1999, 18, 3497–3504. doi: 10.1016/S0277-5387(99)00281-8
24. [24]
  Westin, G.; Norrestam, R.; Nygren, M.; Wijk, M. Synthesis, characterization, and structure determination of a new heterometallic oxoalkoxide: Er₂Ti₄O₂(OC₂H₅)₁₈(HOC₂H₅)₂. J. Solid State Chem. 1998, 135, 149–158. doi: 10.1006/jssc.1997.7616
25. [25]
  Berger, E.; Westin, G. Structure of a hepta-nuclear termetallic oxo-alkoxide: Eu₃K₃TiO₂(OBu^t)₁₁(OMe/OH)(HOBu^t). J. Sol-Gel Sci. Techn. 2010, 53, 681–688. doi: 10.1007/s10971-010-2150-8
26. [26]
  Ojea, M. J. H.; Lorusso, G.; Craig, G. A.; Wilson, C.; Evangelisti, M.; Murrie, M. A topologically unique alternating {Co₃^ⅢGd₃^Ⅲ} magnetocaloric ring. Chem. Commun. 2017, 53, 4799–4802.
27. [27]
  Zhang, G. L.; Wang, S.; Hou, J. L.; Mo, C. J.; Que, C. J.; Zhu, Q. Y.; Dai, J. A lanthanide-titanium (LnTi₁₁) oxo-cluster, a potential molecule based fluorescent labelling agent and photocatalyst. Dalton Trans. 2016, 45, 17681–17686.
28. [28]
  Luo, W.; Hou, J. L.; Zou, D. H.; Cui, L. N.; Zhu, Q. Y.; Dai, J. Lanthanide-titanium-oxalate clusters and their degradation products, photocurrent response and photocatalytic behaviours. New J. Chem. 2018, 42, 11629–11634.
29. [29]
  Huang, C. H.; Sun, H. Y.; Zhang, D. L.; Xu, G. X.; Han, Y. Z.; Shi, N. C. Structure studies on rare earth carboxylate-synthesis and crystal structure study of {dy[(CH₃)₃CCOOl₃(H₂O)₃}[(CH₃)₃CCOOH]₂ (V). Nat. Sci. 1992, 2, 113–118.
30. [30]
  Zheng, Y. Z.; Evangelisti, M.; Winpenny, R. E. P. Co-Gd phosphonate complexes as magnetic refrigerants. Chem. Sci. 2011, 2, 99–102.
31. [31]
  Wendlandt, W. W.; Hecht, H. G. Reflectance spectroscopy, interscience. New York 1966.
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