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Investigation of the separation potential of xanthenyl- and thioxanthenyl-based host compounds for pyridine and isomeric picoline mixtures

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Abstract

Here, the potential of employing trans-N,N′-bis(9-phenyl-9-xanthenyl)cyclohexane-1,2-diamine (1,2-DAX) and trans-N,N′-bis(9-phenyl-9-thioxanthenyl)cyclohexane-1,2-diamine (1,2-DAT) for the purification of various pyridine (PYR), 2-methylpyridine (2MP), 3-methylpyridine (3MP) and 4-methylpyridine (4MP) mixtures, through host–guest chemistry, was investigated. All four solvents were independently clathrated by these host compounds, with a 1:1 host:guest ratio being most favoured. The recrystallization of 1,2-DAX from equimolar mixtures of these guests revealed it to possess an enhanced affinity for 4MP. Furthermore, it was shown that 1,2-DAX may be useful for the separation of solutions of 3MP/PYR, 2MP/PYR and 4MP/2MP; here, host selectivities ranged between 72.9 and 76.6%. The alternative host compound, 1,2-DAT, on the other hand, behaved contrastingly and discriminated significantly against 4MP, whilst preferring the 2-alkylated analogue. Additionally, the selectivity behaviour of 1,2-DAT far exceeded that of 1,2-DAX, and when the solutions were 2MP/4MP, 3MP/4MP and PYR/4MP, very high host selectivities were noted (86.0–94.9%), alluding to the plausibility of using this host compound for these guest separations. Varying the guest amounts in competition experiments confirmed observations from the equimolar investigations. Single crystal X-ray diffraction and thermal analyses were also employed to further analyse the complexes, the reasons for guest retention as well as their relative thermal stabilities. All of our findings are presented here.

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Acknowledgements

Financial support is acknowledged from the Nelson Mandela University and the National Research Foundation (NRF). MRC thanks the University of Cape Town for research support.

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Authors and Affiliations

  1. Department of Chemistry, Nelson Mandela University, PO Box 77000, Port Elizabeth, 6031, South Africa

    Benita Barton, Daniel V. Jooste & Eric C. Hosten

  2. Department of Chemistry, University of Cape Town, Rondebosch, 7701, South Africa

    Mino R. Caira

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  1. Benita Barton
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  2. Mino R. Caira
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  3. Daniel V. Jooste
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  4. Eric C. Hosten
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Correspondence to Benita Barton.

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10847_2020_1023_MOESM1_ESM.docx

Supplementary file1 (DOCX 709 kb)—Supplementary information: Crystallographic data for these novel complexes were deposited at the Cambridge Crystallographic Data Centre {CCDC- 2006097 [1,2-DAX•2(PYR)], 2006098 (1,2-DAX•2MP), 2006099 (1,2-DAX•3MP), 2006100 (1,2-DAX•4MP), 2006101 (1,2-DAT•PYR), 2006102 (1,2-DAT•2MP), 2006103 (1,2-DAT•3MP) and 2006104 [2(1,2-DAT)•3(4MP)]. These data may be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. Figures S1a–c and S2a–h display the void diagrams and overlaid thermal traces for each of the complexes, respectively.

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Barton, B., Caira, M.R., Jooste, D.V. et al. Investigation of the separation potential of xanthenyl- and thioxanthenyl-based host compounds for pyridine and isomeric picoline mixtures. J Incl Phenom Macrocycl Chem 98, 223–235 (2020). https://doi.org/10.1007/s10847-020-01023-9

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