Advertisement

Comparing the effect of selected substituent changes on host ability and selectivity in four xanthenyl-type host compounds in the presence of cyclohexanone and methylcyclohexanone isomers

  • Benita BartonEmail author
  • Lize de Jager
  • Ulrich Senekal
  • Eric C. Hosten
Original Article
  • 55 Downloads

Abstract

Four related xanthenyl and thioxanthenyl host compounds, N,N′-bis(9-phenyl-9-thioxanthenyl)ethylenediamine (H1), N,N′-bis(9-phenyl-9-xanthenyl)ethylenediamine (H2), N,N′-bis(9-cyclohexyl-9-thioxanthenyl)ethylenediamine (H3) and N,N′-bis(9-cyclohexyl-9-xanthenyl)ethylenediamine (H4) were synthesized and compared for their host ability and selectivity in the presence of cyclohexanone and the methylcyclohexanone isomers. Surprisingly, only H1 was an effective host compound in these conditions, clathrating all four potential guest solvents; H2 failed to crystallize from these compounds, while both H3 and H4 included only cyclohexanone, also failing to crystallize from the methylcyclohexanone isomers. H1 was further assessed for any selectivity when presented with mixtures of these guests, and a host selectivity order of 2MeCy (67.6%) > 3MeCy (23.1%) > 4MeCy (9.3%) was observed, while the addition of cyclohexanone to these experiments resulted in an adaptation of this order [Cy (39.2%) = 2MeCy (41.7%) ≫ 3MeCy (13.5%) > 4MeCy (5.6%)]. SCXRD analysis demonstrated that the host packing in H1·Cy, H1·2MeCy and H1·3MeCy was isostructural (monoclinic, P21/n), while H1·4MeCy crystallized in a different crystal system (triclinic, P − 1). All four guests experienced (host)C–H···O–C(guest) interactions, with Cy, a preferred guest, experiencing the shortest of these (2.40 Å, 167°). Thermal analyses showed the preferred guests (cyclohexanone and 2-methylcyclohexanone) to form complexes with enhanced thermal stabilities relative to the other two (3- and 4-methylcyclohexanone) (Tp 129.8 and 99.0 °C vs. 97.9 and 95.3 °C, respectively). This investigation has demonstrated that subtle changes in the structures of these xanthenyl- and thioxanthenyl-type host systems may instigate dramatic host behaviour changes in the presence of these cyclohexanone guest solvents.

Keywords

Cyclohexanone Isomers Host–guest chemistry Inclusion Supramolecular chemistry Xanthenyl 

Notes

Acknowledgements

Financial support is acknowledged from the Nelson Mandela University and the National Research Foundation (NRF). L. Bolo is thanked for thermogravimetric analyses.

References

  1. 1.
    Lehn, J.-M.: Supramolecular Chemistry. Concepts and Perspectives. Wiley, Weinheim (1995).  https://doi.org/10.1002/3527607439 CrossRefGoogle Scholar
  2. 2.
    Atwood, J.L., Steed, J.W.: Encyclopedia of Supramolecular Chemistry, vol. 1. Marcel Dekker Inc., New York (2004)CrossRefGoogle Scholar
  3. 3.
    Steed, J.W., Turner, D.R., Wallace, K.: Core Concepts in Supramolecular Chemistry and Nanochemistry. Wiley, Weinheim (2007)Google Scholar
  4. 4.
    Nassimbeni, L.R., Samipillai, M., Batisai, E., Weber, E.: Separation of lutidines by enclathration. CrystEngComm 17, 8332 (2015)CrossRefGoogle Scholar
  5. 5.
    Seebach, D., Beck, A.K., Heckel, A.: TADDOLs, their derivatives, and TADDOL analogues: versatile chiral auxiliaries. Angew. Chem. Int. Ed. 40, 92 (2001)CrossRefGoogle Scholar
  6. 6.
    Feng, J., Yang, G., Meia, Y., Cao, X., Wang, Y., Li, H., Lu, Q.: Macroscopic visual detection of phoxim by calix[4]arene-based host-guest chemistry. Sens. Actuators B 271, 264 (2018)CrossRefGoogle Scholar
  7. 7.
    Yin, M., Gu, B., An, Q., Yang, C., Guan, Y.L., Yong, K.-T.: Recent development of fiber-optic chemical sensors and biosensors: mechanisms, materials, micro/nano-fabrications and applications. Coord. Chem. Rev. 376, 348 (2018)CrossRefGoogle Scholar
  8. 8.
    Lv, P., Zhang, D., Guo, M., Liuc, J., Chen, X., Guo, R., Xu, Y., Zhang, Q., Liu, Y., Guo, H., Yang, M.: Structural analysis and cytotoxicity of host-guest inclusion complexes of cannabidiol with three native cyclodextrins. J. Drug Deliv. Sci. Technol. 51, 337 (2019)CrossRefGoogle Scholar
  9. 9.
    Tang, P., Sun, Q., Suo, Z., Zhao, L., Yang, H., Xiong, X., Pu, H., Gan, N., Li, H.: Rapid and efficient removal of estrogenic pollutants from water by using beta- and gamma-cyclodextrin polymers. Chem. Eng. J. 344, 514 (2018)CrossRefGoogle Scholar
  10. 10.
    Barton, B., de Jager, L., Hosten, E.C.: An investigation of the complexation of host N,N′-bis(9-phenyl-9-thioxanthenyl)ethylenediamine with dihaloalkanes guests. J. Incl. Phenom. Macrocyclic Chem. 89, 105 (2017)CrossRefGoogle Scholar
  11. 11.
    Barton, B., Caira, M.R., de Jager, L., Hosten, E.C.: N, N′-Bis(9-phenyl-9-thioxanthenyl)ethylenediamine: highly selective host behavior in the presence of xylene and ethylbenzene guest mixtures. Cryst. Growth Des. 17, 6660 (2017)CrossRefGoogle Scholar
  12. 12.
    Barton, B., de Jager, L., Hosten, E.C.: Host proficiency of N,N′-bis(9-phenyl-9-thioxanthenyl)ethylenediamine for pyridine and the methylpyridine guests—a competition study. Supramol. Chem. 30, 61 (2018)CrossRefGoogle Scholar
  13. 13.
    Barton, B., de Jager, L., Hosten, E.C.: A comparison of the behaviour of two closely related xanthenyl-derived host compounds in the presence of vaporous dihaloalkanes. J. Incl. Phenom. Macrocycl. Chem. 92(1), 181 (2018)Google Scholar
  14. 14.
    Barton, B., de Jager, L., Hosten, E.C.: Host behaviour of N,N′-Bis(9-phenyl-9-thioxanthenyl)ethylenediamine in the presence of aromatic and aliphatic five-membered heterocyclic guests: selectivity correlations with Hirshfeld surface analyses. Cryst. Growth Des. 19, 1268 (2019)CrossRefGoogle Scholar
  15. 15.
    Barton, B., McCleland, C.W., Caira, M.R., de Jager, L., Hosten, E.C.: Crystal X-ray diffraction and molecular modelling considerations elucidate the factors responsible for the opposing host behaviour of two isostructural xanthenyl- and thioxanthenyl- derived host compounds. Cryst. Growth Des. 19, 2396 (2019)CrossRefGoogle Scholar
  16. 16.
    Barton, B., de Jager, L., Hosten, E.C.: Minor modifications afford improved host selectivities in xanthenyl-type host systems. CrystEngComm (2019).  https://doi.org/10.1039/c9ce00265k CrossRefGoogle Scholar
  17. 17.
    Barton, B., Senekal, U., Hosten, E.C.: Compounds N,N′-bis(9-cyclohexyl-9-xanthenyl)ethylenediamine and its thio derivative, N,N′-bis(9-cyclohexyl-9-thioxanthenyl)ethylenediamine, as potential hosts in the presence of xylenes and ethylbenzene: conformational analyses and molecular modelling considerations. Tetrahedron 2, 2 (2019).  https://doi.org/10.1016/j.tet.2019.04.065 CrossRefGoogle Scholar
  18. 18.
    Barton B.: Host-guest chemistry: the synthesis and assessment of host compounds based on the 9-arylxanthenyl and related systems, PhD thesis, University of Port Elizabeth, Port Elizabeth (1997)Google Scholar
  19. 19.
    Mercury 3.10.2 (Build 189770), http://www.ccdc.cam.ac.uk/mercury/ [Accessed 2019.]
  20. 20.
    Bruker, A.: APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, WI (2007)Google Scholar
  21. 21.
    Sheldrick, G.M.: SHELXT-integrated space-group and crystal-structure determination. Acta Crystallogr. A 71, 3 (2015)CrossRefGoogle Scholar
  22. 22.
    Sheldrick, G.M.: Crystal structure refinement with SHELXL. Acta Crystallogr. C 71, 3 (2015)CrossRefGoogle Scholar
  23. 23.
    Hübschle, C.B., Sheldrick, G.M., Dittrich, B.: ShelXle: a Qt graphical user interface for SHELXL. J. Appl. Crystallogr. 44, 1281 (2011)CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.Department of ChemistryNelson Mandela UniversityPort ElizabethSouth Africa

Personalised recommendations