Home Physical Sciences Natural Abundance Nitrogen-15 NMR in Thermotropic Liquid Crystals With Cyano-Group
Article
Licensed
Unlicensed Requires Authentication

Natural Abundance Nitrogen-15 NMR in Thermotropic Liquid Crystals With Cyano-Group

  • Lukas Jackalin and Sergey V. Dvinskikh EMAIL logo
Published/Copyright: October 5, 2016

Abstract

We present natural abundance nitrogen-15 (NAN15) NMR spectroscopy in thermotropic liquid crystals. It is demonstrated that high resolution NAN15 NMR spectra in mesophases can be accurately recorded in non-spinning samples with a high orientational molecular order and strong anisotropic spin interactions. In this technique, due to low demand on radio-frequency decoupling power, standard solution-state probes can be used, which generally provide superior sensitivity and spectroscopic resolution in comparison to solid-state probes. We show that 15N chemical shift anisotropy (CSA) can be used as a sensitive probe of molecular orientational dynamics in liquid crystals. This method is exploited here to measure the orientational molecular order parameter of the nematic 4-pentyl-4′-cyanobiphenyl (5CB). Since the nitrogen spectra are obtained from the molecules constituting the mesophase rather than from probe molecules, the information is direct and the analysis and interpretation is straightforward. Nitrogen CSA of immobilized molecules, required in the analysis, is obtained using a DFT calculation. The approach provided consistent results for the order parameter in the nematic 5CB in the whole temperature range, in good agreement with literature data.


Dedicated to: Kev Salikhov on the occasion of his 80th birthday.


Acknowledgments

L. J. acknowledges KTH fund for summer studentship. We thank Björn Dahlgren (KTH) and Tore Brinck (KTH) for support with DFT analysis.

References

1. R. Y. Dong, Nuclear magnetic resonance spectroscopy of liquid crystals, London: Worlds Scientific, 2010.10.1142/7310Search in Google Scholar

2. P. G. de Gennes, J. Prost, The physics of liquid crystals, Oxford: Clarendon, 1993.10.1093/oso/9780198520245.001.0001Search in Google Scholar

3. B. M. Fung, Prog. Nucl. Magn. Reson. Spectrosc. 41 (2002) 171.10.1016/S0079-6565(02)00048-1Search in Google Scholar

4. S. V. Dvinskikh, D. Sandström, H. Zimmermann, A. Maliniak, Progr. Nucl. Magn. Reson. Spectrosc. 48 (2006) 85.10.1016/j.pnmrs.2005.12.002Search in Google Scholar

5. H. Zimmermann, Liq. Cryst. 4 (1989) 591.10.1080/02678298908033195Search in Google Scholar

6. P. Lesot, J. Courtieu, Progr. Nucl. Magn. Reson. Spectr. 55 (2009) 128.10.1016/j.pnmrs.2009.01.001Search in Google Scholar

7. D. Sandström, H. Zimmermann, J. Phys. Chem. B 104 (2000) 1490.10.1021/jp9938765Search in Google Scholar

8. M. Witanowski, G. A. Webb, Nitrogen NMR, London: Plenum Press (1973).10.1007/978-1-4684-8175-4Search in Google Scholar

9. I. Schnell, K. Saalwächter, J. Am. Chem. Soc. 124 (2002) 10938.10.1021/ja026657xSearch in Google Scholar PubMed

10. A. Lesage, P. Charmont, S. Steuernagel, L. Emsley, J. Am. Chem. Soc. 122 (2000) 9739.10.1021/ja0018320Search in Google Scholar

11. M. I. B. Tavares, C. M. G. de Souza, J. Appl. Polym. Sci. 90 (2003) 3872.10.1002/app.13108Search in Google Scholar

12. P. M. Aguiar, M. J. Katz, D. B. Leznoff, S. Kroeker, Phys. Chem. Chem. Phys. 11 (2009) 6925.10.1039/b907747bSearch in Google Scholar PubMed

13. P. Palmas, S. Ilas, E. Girard, Magn. Reson. Chem. 49 (2011) 788.10.1002/mrc.2834Search in Google Scholar PubMed

14. A. Höhener, L. Müller, R. R. Ernst, Mol. Phys. 38 (1979) 909.10.1080/00268977900102131Search in Google Scholar

15. M. Giese, J. C. De Witt, K. E. Shopsowitz, A. P. Manning, R. Y. Dong, C. A. Michal, W. Y. Hamad, M. J. MacLachlan, ACS Appl. Mater. Interfaces 5 (2013) 6854.10.1021/am402266zSearch in Google Scholar PubMed

16. A. P. Manning, M. Giese, A. S. Terpstra, M. J. MacLachlan, W. Y. Hamad, R. Y. Dong, C. A. Michal, Magn. Reson. Chem. 52 (2014) 532.10.1002/mrc.4101Search in Google Scholar PubMed

17. D. Demus, H. Zaschke, Flüssige kristalle in Tabellen II, Leipzig: VEB Deutscher Verlag für Grundstoffindustrie, (1984).Search in Google Scholar

18. A. R. Kortan, H. V. Kanel, R. J. Birgeneau, J. D. Litster, Phys. Rev. Lett. 47 (1981) 1206.10.1103/PhysRevLett.47.1206Search in Google Scholar

19. P. E. Cladis, Liq. Cryst. 24 (1998) 15.10.1080/026782998207532Search in Google Scholar

20. S. V. Dvinskikh, I. Furo, Phys. Rev. E 86 (2012) 031704.10.1103/PhysRevE.86.031704Search in Google Scholar PubMed

21. P. Bertani, J. Raya, B. Bechinger, Solid State Nucl. Magn. Reson. 61–62 (2014) 15.10.1016/j.ssnmr.2014.03.003Search in Google Scholar PubMed

22. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C.; Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox, ‘Gaussian 09, Revision A.02’, Wallingford CT: Gaussian, Inc. (2009).Search in Google Scholar

23. A. D. Becke, J. Chem. Phys. 98 (1993) 5648.10.1063/1.464913Search in Google Scholar

24. J. R. Cheeseman, G. W. Trucks, T. A. Keith, M. J. Frisch, J. Chem. Phys. 104 (1996) 5497.10.1063/1.471789Search in Google Scholar

25. R. Ditchfield, Mol. Phys. 27 (1974) 789.10.1080/00268977400100711Search in Google Scholar

26. T. Van Voorhis, G. E. Scuseria, J. Chem. Phys. 109 (1998) 400.10.1063/1.476577Search in Google Scholar

27. B. M. Fung, A. K. Khitrin, K. Ermolaev, J. Magn. Reson. 142 (2000) 97.10.1006/jmre.1999.1896Search in Google Scholar PubMed

28. A. E. Bennett, C. M. Rienstra, M. Auger, K. V. Lakshmi, R. G. Griffin, J. Chem. Phys. 103 (1995) 6951.10.1063/1.470372Search in Google Scholar

29. S. V. Dvinskikh, I. Furó, Russ. Chem. Rev. 75 (2006) 497.10.1070/RC2006v075n06ABEH003635Search in Google Scholar

30. S. V. Dvinskikh, I. Furó, H. Zimmermann, A. Maliniak, Phys. Rev. E 65 (2002) 061701.10.1103/PhysRevE.65.061701Search in Google Scholar PubMed

31. J. W. Emsley, P. Lesot, G. De Luca, A. Lesage, D. Merlet, G. Pileio, Liq. Cryst. 35 (2008) 443.10.1080/02678290801935887Search in Google Scholar

32. E. D. Gerts, A. V. Komolkin, V. A. Burmistrov, V. V. Alexandriysky, S. V. Dvinskikh, J. Chem. Phys. 141 (2014) 074503.10.1063/1.4892877Search in Google Scholar PubMed

33. J. W. Emsley, Nuclear magnetic resonance of liquid crystals, Dordrecht: Reidel (1985).10.1007/978-94-009-6517-1Search in Google Scholar

34. S. V. Dvinskikh, D. Sandström, H. Zimmermann, A. Maliniak, 13C NMR studies of columnar liquid crystals, in New Research on Magnetic Resonance, ed. by B. C. Castleman, New York: Nova Science Publisher (2007), p. 189.Search in Google Scholar

35. M. Sardashti, G. E. Maciel, J. Phys. Chem. 92 (1988) 4620.10.1021/j100327a013Search in Google Scholar

36. R. G. Horn, J. Phys. (France) 39 (1978) 105.10.1051/jphys:01978003901010500Search in Google Scholar

37. I. Haller, Prog. Solid State Chem. 10 (1975) 103.10.1016/0079-6786(75)90008-4Search in Google Scholar

38. M. J. Duer, Introduction to solid-state NMR spectroscopy, Oxford: Blackwell, 2005.Search in Google Scholar

39. F. H. Allen, O. Kennard, D. G. Watson, L. Brammer, A. G. Orpen, R. Taylor, J. Chem. Soc. Perkin Trans. 2 (1987) S1.10.1039/p298700000s1Search in Google Scholar

40. N. J. D. Lucas, Mol. Phys. 22 (1971) 147.10.1080/00268977100102411Search in Google Scholar

Received: 2016-6-12
Accepted: 2016-9-4
Published Online: 2016-10-5
Published in Print: 2017-4-1

©2017 Walter de Gruyter GmbH, Berlin/Boston

Downloaded on 7.12.2025 from https://www.degruyterbrill.com/document/doi/10.1515/zpch-2016-0814/html?lang=en
Scroll to top button