Synthesis, Characterization, and Crystal Structure of Lithium Pyrrolide

Jing Zijun ^1,2, ,
Khai Chen Tan ^1,2, ,
He Teng ^{1,
,} ,
Yu Yang ^1,2, ,
Pei Qijun ^1,2, ,
Wang Jintao ^1,2, ,
Wu Hui ^{3,
,} ,
Chen Ping ^1,

1.
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China
3.
NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, MD 20899-6102, USA

Corresponding author: He Teng, heteng@dicp.ac.cn Wu Hui, huiwu@nist.gov

Received Date: 10 September 2020
Accepted Date: 19 October 2020
Revised Date: 19 October 2020
Available Online: 15 November 2021
Fund Project:
the K. C. Wong Education Foundation GJTD-2018-06

the National Natural Science Foundation of China 51671178

The project was supported by the National Key R&D Program of China (2018YFB1502100, 2019YFE0103600), the National Natural Science Foundation of China (51671178, 51472237), the Light Source Fund of Dalian Institute of Chemical Physics, Chinese Academy of Sciences (DICP DCLS201701), the Liaoning Revitalization Talents Program (XLYC1807157), and the K. C. Wong Education Foundation (GJTD-2018-06)

the Liaoning Revitalization Talents Program XLYC1807157

the National Natural Science Foundation of China 51472237

the National Key R&D Program of China 2018YFB1502100

the Light Source Fund of Dalian Institute of Chemical Physics, Chinese Academy of Sciences DICP DCLS201701

the National Key R&D Program of China 2019YFE0103600

Abstract: Development of clean energy is an urgent requirement because of the depletion of fossil energy sources and increasingly severe environmental pollution. However, the lack of safe and efficient hydrogen storage materials is one of the bottlenecks in the implementation of hydrogen energy. Liquid organic hydrogen carriers (LOHCs) have been recognized as potential materials for the storage and transportation of hydrogen owing to their high gravimetric and volumetric hydrogen densities, reversible hydrogen absorption and desorption ability, and ease of widespread implementation with minimal modification on the existing fueling infrastructure. While some LOHCs such as cycloalkanes and N-heterocycles have been developed for hydrogen storage, they require a high hydrogen release temperature due to the large enthalpy change of dehydrogenation. In our previous work, a metallation strategy was proposed to improve the thermodynamic properties of liquid organic hydrogen carriers for hydrogen storage, and a series of metalorganic hydrides were synthesized and investigated. Among them, sodium phenoxide-cyclohexanolate pair, lithium carbazolide-perhydrocarbazolide, and sodium anilinide-cyclohexylamide pair showed promising dehydrogenation thermodynamics and improved hydrogen storage properties. Sodium pyrrolide and sodium imidazolide were also synthesized. However, pyrrolides were not well characterized, and the structure of lithium pyrrolide was not resolved. In the present study, we synthesized sodium and lithium pyrrolides by ball milling and wet chemical methods. One equivalent of hydrogen could be released from the reaction of pyrrole and metal hydrides, indicating the replacement of H by metal. The formation of pyrrolides was confirmed by nuclear magnetic resonance (NMR), X-ray diffraction (XRD) and ultraviolet-visible spectroscopy analyses. The ¹H signals attributed to C－H in the NMR spectra of the alkali metal pyrrolides shifted upfield due to the replacement of the H of N－H with a stronger electron-donating species (Li or Na), resulting in a greater shielding environment upon metallation. The absorption peaks of lithium and sodium pyrrolides showed red shifts, and the intensities became obviously stronger in the UV-Vis spectra, suggesting an enhancement of the conjugation effect, in accordance with theoretical calculations. The structure of lithium pyrrolide was determined by the combined direct space method and first-principles calculations on XRD data and Rietveld refinement. This molecule crystallizes in the monoclinic P2₁/c (14) space group, with lattice parameters of a = 4.4364(7) Å, b = 11.969(2) Å, c = 8.192(2) Å, β = 108.789(8)°, and V = 411.8(2) Å³ (1 Å = 0.1 nm). Each Li⁺ cation is surrounded by three pyrrolides via cation－N σ bonding with two pyrrolides and a cation–π interaction with the third pyrrolide, where the Li⁺ is on the top of the π face. Our experimental findings are different from the theoretical prediction in the literature.

Key words:

1. [1]
  He, T.; Pachfule, P.; Wu, H.; Xu, Q.; Chen, P. Nat. Rev. Mater. 2016, 1(12), 16059. doi: 10.1038/natrevmats.2016.59
2. [2]
  Zhu, Q. L.; Xu, Q. Energy Environ. Sci. 2015, 8(2), 478. doi: 10.1039/C4EE03690E
3. [3]
  Sakintuna, B.; Lamari-Darkrim, F.; Hirscher, M. Int. J. Hydrogen Energy 2007, 32(9), 1121. doi: 10.1016/j.ijhydene.2006.11.022
4. [4]
  Gutowska, A.; Li, L.; Shin, Y.; Wang, C. M.; Li, X. S.; Linehan, J. C.; Smith, R. S.; Kay, B. D.; Schmid, B.; Shaw, W.; et al. Angew. Chem. 2005, 117(23), 3644. doi: 10.1002/ange.200462602
5. [5]
  Xiong, Z.; Yong, C. K.; Wu, G.; Chen, P.; Shaw, W.; Karkamkar, A.; Autrey, T.; Jones, M. O.; Johnson, S. R.; Edwards, P. P.; David, W. I. F. Nat. Mater. 2008, 7(2), 138. doi: 10.1038/nmat2081
6. [6]
  Bogdanović, B.; Schwickardi, M. J. Alloys Compd. 1997, 253–254, 1. doi: 10.1016/S0925-8388(96)03049-6
7. [7]
  Chen, P.; Xiong, Z.; Luo, J.; Lin, J.; Tan, K. L. Nature 2002, 420(6913), 302. doi: 10.1038/nature01210
8. [8]
  Züttel, A.; Wenger, P.; Rentsch, S.; Sudan, P.; Mauron, P.; Emmenegger, C. J. Power Sources 2003, 118(1), 1. doi: 10.1016/S0378-7753(03)00054-5
9. [9]
  肖学章, 陈立新, 王新华, 李寿权, 陈长聘.物理化学学报, 2006, 22(12), 1511. doi: 10.3866/PKU.WHXB20061215Xiao, X.; Chen, L.; Wang, X.; Li, S.; Chen, C. Acta Phys. -Chim. Sin. 2006, 22(12), 1511. doi: 10.3866/PKU.WHXB20061215
10. [10]
  Modisha, P. M.; Ouma, C. N. M.; Garidzirai, R.; Wasserscheid, P.; Bessarabov, D. Energy Fuels 2019, 33(4), 2778. doi: 10.1021/acs.energyfuels.9b00296
11. [11]
  Müller, K.; Thiele, S.; Wasserscheid, P. Energy Fuels 2019, 33(10), 10324. doi: 10.1021/acs.energyfuels.9b01939
12. [12]
  Preuster, P.; Papp, C.; Wasserscheid, P. Acc. Chem. Res. 2017, 50(1), 74. doi: 10.1021/acs.accounts.6b00474
13. [13]
  Yang, J.; Sudik, A.; Wolverton, C.; Siegel, D. J. Chem. Soc. Rev. 2010, 39(2), 656. doi: 10.1039/B802882F
14. [14]
  Clot, E.; Eisenstein, O.; Crabtree, R. H. Chem. Commun. 2007, No. 22, 2231. doi: 10.1039/B705037B
15. [15]
  Pez, G. P.; Scott, A. R.; Cooper, A. C.; Cheng, H. Hydrogen storage by reversible hydrogenation of pi-conjugated substrates. US Patent US07101530, 2006.
16. [16]
  Cui, Y.; Kwok, S.; Bucholtz, A.; Davis, B.; Whitney, R. A.; Jessop, P. G. New J. Chem. 2008, 32(6), 1027. doi: 10.1039/B718209K
17. [17]
  Jing, Z.; Yu, Y.; Chen, R.; Tan, K. C.; He, T.; Wu, A.; Pei, Q.; Chua, Y. S.; Zheng, D.; Zhang, X.; et al. Chem. Commun. 2020, 56(13), 1944. doi: 10.1039/C9CC08593A
18. [18]
  Tan, K. C.; Yu, Y.; Chen, R.; He, T.; Jing, Z.; Pei, Q.; Wang, J.; Chua, Y. S.; Wu, A.; Zhou, W.; et al. Energy Storage Mater. 2020, 26, 198. doi: 10.1016/j.ensm.2019.12.035
19. [19]
  Yu, Y.; He, T.; Wu, A.; Pei, Q.; Karkamkar, A.; Autrey, T.; Chen, P. Angew. Chem. Int. Ed. 2019, 58(10), 3102. doi: 10.1002/anie.201810945
20. [20]
  Blanco, F.; Alkorta, I.; Elguero, J. J. Phys. Chem. A 2008, 112(33), 7682. doi: 10.1021/jp801936v
21. [21]
  Ruan, C.; Yang, Z.; Rodgers, M. T. Int. J. Mass Spectrom. 2007, 267(1), 233. doi: 10.1016/j.ijms.2007.02.041
22. [22]
  Scott, M. S.; Lucas, A. C.; Luckhurst, C. A.; Prodger, J. C.; Dixon, D. J. Org. Biomol. Chem. 2006, 4(7), 1313. doi: 10.1039/B515356E
23. [23]
  Baltazzi, E.; Krimen, L. I. Chem. Rev. 1963, 63(5), 511. doi: 10.1021/cr60225a004
24. [24]
  Yu, G.; Huang, X. R.; Chen, W.; Sun, C. C. J. Comput. Chem. 2011, 32(9), 2005. doi: 10.1002/jcc.21789
25. [25]
  Goddard, R.; Heinemann, O.; Krüger, C. Acta Cryst. 1997, 53(12), 1846. doi: 10.1107/S0108270197009682

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