Noria and its derivatives as hosts for chemically and thermally robust Type II porous liquids
Noria and its derivatives as hosts for chemically and thermally robust Type II porous liquids
Porous Liquids (PLs) are a new class of material that possess both fluidity and permanent porosity. As such they can act as enhanced, selective solvents and may ultimately find applications which are not possible for porous solids, such as continuous flow separation processes. Type II PLs consist of empty molecular hosts dissolved in size-excluded solvents and to date have mainly been based on hosts that have limited chemical and thermal stability. Here we identify Noria, a rigid cyclic oligomer as a new host for the synthesis of more robust Type II PLs. Although the structure of Noria is well-documented, we find that literature has overlooked the true composition of bulk Noria samples. We find that bulk samples typically consist of Noria (ca. 40%), a Noria isomer, specifically a resorcinarene trimer, “R3” (ca. 30%) and other unidentified oligomers (ca. 30%). Noria has been characterised crystallographically as a diethyl ether solvate and its 1H NMR spectrum fully assigned for the first time. The previously postulated but unreported R3 has also been characterised crystallographically as a dimethyl sulfoxide solvate, which confirms its alternative connectivity to Noria. Noria and R3 have low solubility which precludes their use in Type II PLs, however, the partially ethylated derivative Noria-OEt dissolves in the size-excluded solvent 15-crown-5 to give a new Type II PL. This PL exhibits enhanced uptake of methane (CH4) gas supporting the presence of empty pores in the liquid. Detailed molecular dynamics simulations support the existence of pores in the liquid and show that occupation of the pores by CH4 is favoured. Overall, this work revises the general accepted composition of bulk Noria samples and shows that Noria derivatives are appropriate for the synthesis of more robust Type II PLs.
14230-14240
Alexander, Francesca M.
dfd50784-8bf0-450f-8cbb-cf1e355eff55
Fonrouge, Sergio F.
92183cdd-239d-46e1-a9c2-ec75a30b2bb4
Borioni, José L.
5fd42c6a-71da-448c-b72a-4c6f16579350
Del Pópolo, Mario G.
e2acde08-cdb9-4ce8-99ba-376012debd74
Horton, Peter
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Hutchings, Benjamin P.
17f0d6ee-a228-42ca-adc7-8eae0cfc5369
Crawford, Deborah E.
e3e2746e-b318-477c-824d-a9ddd9ffa039
James, Stuart L.
64b3fff6-707c-4523-823b-e4890ed07b18
14 October 2021
Alexander, Francesca M.
dfd50784-8bf0-450f-8cbb-cf1e355eff55
Fonrouge, Sergio F.
92183cdd-239d-46e1-a9c2-ec75a30b2bb4
Borioni, José L.
5fd42c6a-71da-448c-b72a-4c6f16579350
Del Pópolo, Mario G.
e2acde08-cdb9-4ce8-99ba-376012debd74
Horton, Peter
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Hutchings, Benjamin P.
17f0d6ee-a228-42ca-adc7-8eae0cfc5369
Crawford, Deborah E.
e3e2746e-b318-477c-824d-a9ddd9ffa039
James, Stuart L.
64b3fff6-707c-4523-823b-e4890ed07b18
Alexander, Francesca M., Fonrouge, Sergio F., Borioni, José L., Del Pópolo, Mario G., Horton, Peter, Coles, Simon J., Hutchings, Benjamin P., Crawford, Deborah E. and James, Stuart L.
(2021)
Noria and its derivatives as hosts for chemically and thermally robust Type II porous liquids.
Chemical Science, 12 (42), .
(doi:10.1039/D1SC03367K).
Abstract
Porous Liquids (PLs) are a new class of material that possess both fluidity and permanent porosity. As such they can act as enhanced, selective solvents and may ultimately find applications which are not possible for porous solids, such as continuous flow separation processes. Type II PLs consist of empty molecular hosts dissolved in size-excluded solvents and to date have mainly been based on hosts that have limited chemical and thermal stability. Here we identify Noria, a rigid cyclic oligomer as a new host for the synthesis of more robust Type II PLs. Although the structure of Noria is well-documented, we find that literature has overlooked the true composition of bulk Noria samples. We find that bulk samples typically consist of Noria (ca. 40%), a Noria isomer, specifically a resorcinarene trimer, “R3” (ca. 30%) and other unidentified oligomers (ca. 30%). Noria has been characterised crystallographically as a diethyl ether solvate and its 1H NMR spectrum fully assigned for the first time. The previously postulated but unreported R3 has also been characterised crystallographically as a dimethyl sulfoxide solvate, which confirms its alternative connectivity to Noria. Noria and R3 have low solubility which precludes their use in Type II PLs, however, the partially ethylated derivative Noria-OEt dissolves in the size-excluded solvent 15-crown-5 to give a new Type II PL. This PL exhibits enhanced uptake of methane (CH4) gas supporting the presence of empty pores in the liquid. Detailed molecular dynamics simulations support the existence of pores in the liquid and show that occupation of the pores by CH4 is favoured. Overall, this work revises the general accepted composition of bulk Noria samples and shows that Noria derivatives are appropriate for the synthesis of more robust Type II PLs.
Text
d1sc03367k
- Version of Record
More information
Submitted date: 21 June 2021
Accepted/In Press date: 10 October 2021
Published date: 14 October 2021
Additional Information:
Funding Information:
We acknowledge the National Mass Spectrometry Facility (NMSF) at Swansea University and in particular the useful discussions had with Dr Ann P. Hunter and Dr Mark F. Wyatt. MGDP acknowledges financial support from SECTyP-UNCUYO, ANPCyT (PICT-2015-1835), and SNCAD for computer time in the clusters Mendieta (CCAD-UNC) and Toko (UNCUYO). We also acknowledge funding from EPSRC, grant number: EP/R005540/1.
Funding Information:
We acknowledge the National Mass Spectrometry Facility (NMSF) at Swansea University and in particular the useful discussions had with Dr Ann P. Hunter and Dr Mark F. Wyatt. MGDP acknowledges nancial support from SECTyP-UNCUYO, ANPCyT (PICT-2015-1835), and SNCAD for computer time in the clusters Mendieta (CCAD-UNC) and Toko (UNCUYO). We also acknowledge funding from EPSRC, grant number: EP/R005540/ 1.
Publisher Copyright:
© The Royal Society of Chemistry 2021.
Copyright:
Copyright 2021 Elsevier B.V., All rights reserved.
Identifiers
Local EPrints ID: 452293
URI: http://eprints.soton.ac.uk/id/eprint/452293
ISSN: 1478-6524
PURE UUID: 0a088f82-fbd3-4ba8-a5e1-82638f693f13
Catalogue record
Date deposited: 03 Dec 2021 17:32
Last modified: 06 Jun 2024 01:38
Export record
Altmetrics
Contributors
Author:
Francesca M. Alexander
Author:
Sergio F. Fonrouge
Author:
José L. Borioni
Author:
Mario G. Del Pópolo
Author:
Peter Horton
Author:
Benjamin P. Hutchings
Author:
Deborah E. Crawford
Author:
Stuart L. James
Download statistics
Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.
View more statistics