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Synthesis and assessment of compounds trans-N,N′-bis(9-phenyl-9-xanthenyl)cyclohexane-1,4-diamine and trans-N,N′-bis(9-phenyl-9-thioxanthenyl)cyclohexane-1,4-diamine as hosts for potential xylene and ethylbenzene guests

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Abstract

In this work, two novel compounds, trans-N,N′-bis(9-phenyl-9-xanthenyl)cyclohexane-1,4-diamine 1 and trans-N,N′-bis(9-phenyl-9-thioxanthenyl)cyclohexane-1,4-diamine 2, were designed and successfully synthesized in our laboratories, and assessed for their host potential in the presence of potential xylene (Xy) isomer and ethylbenzene (EB) guests. Host 1 successfully formed complexes with all four of o-Xy, m-Xy, p-Xy and EB, while 2 only clathrated p-Xy and EB. Equimolar guest/guest competition experiments showed that hosts 1 and 2 possess very similar selectivities for these guests [p-Xy (73.9%) > EB (13.0%) > m-Xy (8.1%) > o-Xy (5.0%) and p-Xy (71.3%) > EB (20.2%) > m-Xy (6.0%) > o-Xy (2.5%) for 1 and 2, respectively]. Single crystal diffraction analyses revealed striking geometry changes for the sulfur host analogue: while the tricyclic fused ring system of the oxygen host remained planar when guest was absent or present, this fused system of the sulfur analogue experienced a dramatic geometry change from buckled (in the absence of guest) to planar (in guest presence). This observation explained the selectivity similarities of both hosts in the presence of these guests. Additionally, the relative thermal stabilities of the four complexes with host 1 were assessed by employing thermal analyses, and the results of these correlated exactly with the selectivity order, since the onset temperature of the guest release processes (Ton) was in the order p-Xy (88.0 °C) > EB (70.9 °C) > m-Xy (59.7 °C) > o-Xy (46.2 °C). Ton values also explained the significant preference of host 2 for p-Xy (115.5 °C) relative to EB (76.6 °C), respectively.

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Acknowledgements

Financial support is acknowledged from the Nelson Mandela University and the National Research Foundation (NRF).

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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

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  1. Benita Barton
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  2. Daniel V. Jooste
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  3. Eric C. Hosten
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Correspondence to Benita Barton.

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10847_2019_883_MOESM1_ESM.docx

Supplementary material Crystallographic data for both the novel host materials 1 and 2 as well as the six complexes were deposited at the Cambridge Crystallographic Data Centre (CCDC reference numbers 1: 1876416, 2: 1876417, 1·o-Xy: 1876418, 1·m-Xy: 1876419, 1·p-Xy: 1876420, 1·EB: 1876421, 2·p-Xy: 1876422 and 2·EB: 1876423). The Supplementary information contains more comprehensive tables that summarize the various host−host and host−guest interactions for hosts 1 (Table S1) and 2 (Table S2), as well as relevant 1H-NMR, 13C-NMR and IR spectra (Figures S1−S16). (DOCX 549 KB)

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Barton, B., Jooste, D.V. & Hosten, E.C. Synthesis and assessment of compounds trans-N,N′-bis(9-phenyl-9-xanthenyl)cyclohexane-1,4-diamine and trans-N,N′-bis(9-phenyl-9-thioxanthenyl)cyclohexane-1,4-diamine as hosts for potential xylene and ethylbenzene guests. J Incl Phenom Macrocycl Chem 93, 333–346 (2019). https://doi.org/10.1007/s10847-019-00883-0

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