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Porous macromolecular dihydropyridyl frameworks exhibiting catalytic and halochromic activity

Xiao, Bo; Easun, Timothy L.; Dhakshinamoorthy, Amarajothi; Cebula, Izabela; Beton, Peter H.; Titman, Jeremy J.; Garcia, Hermenegildo; Thomas, K. Mark; Schröder, Martin

Authors

Bo Xiao

Timothy L. Easun

Amarajothi Dhakshinamoorthy

Izabela Cebula

Hermenegildo Garcia

K. Mark Thomas

Martin Schröder M.Schroder@man.ac.uk



Abstract

New porous macromolecular frameworks (PMFs) have been designed and prepared by the condensation of dialdehydes with aminoacrylonitriles. Two porous materials were prepared by reacting 3,3′-benzene-1,4-diylbis(3-aminoprop-2-enenitrile) with benzene-1,4-dicarbaldehyde and biphenyl-4,4′-dicarbaldehyde to give PMF-NOTT-1 and PMF-NOTT-2, respectively. Adsorption and desorption studies of N2 (77 K) and CO2 (273–303 K and 20 bar) were used to characterize the porosity of these materials. CO2 adsorption measurements indicate that these PMFs have similar porosity with Dubinin–Radushkevich micropore volumes of 0.142 and 0.144 cm3 g−1 and CO2 surface excess uptakes of 28.4 and 28.9 wt% at 20 bar, 273 K for PMF-NOTT-1 and PMF-NOTT-2, respectively. The isosteric heats of adsorption for CO2 at zero surface coverage were 31.9 kJ mol−1 (for PMF-NOTT-1) and 33.1 kJ mol−1 (for PMF-NOTT-2). However, N2 adsorption studies at 77 K indicated that PMF-NOTT-2 shows activated diffusion effects due to the presence of some narrow ultramicroporosity. The conjugated systems of these frameworks can be reversibly switched by varying proton concentration in solution and these materials thus demonstrate halochromic properties. PMF-NOTT-1, constructed from shorter building blocks than PMF-NOTT-2, exhibits higher catalytic activity and selectivity in Knoevenagel condensation reactions of malononitrile with benzaldehydes. The advantages of using PMFs as catalysts or adsorbents are their excellent thermal and chemical stabilities and they can be recovered and regenerated for re-use.

Journal Article Type Article
Publication Date Oct 28, 2014
Journal Journal of Materials Chemistry A
Print ISSN 2050-7488
Electronic ISSN 2050-7496
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 2
Issue 46
Pages 19889-19896
APA6 Citation Xiao, B., Easun, T. L., Dhakshinamoorthy, A., Cebula, I., Beton, P. H., Titman, J. J., …Schröder, M. (2014). Porous macromolecular dihydropyridyl frameworks exhibiting catalytic and halochromic activity. Journal of Materials Chemistry A, 2(46), 19889-19896. https://doi.org/10.1039/c4ta02521k
DOI https://doi.org/10.1039/c4ta02521k
Keywords porous macromolecular frameworks, PMFs, dialdehydes, aminoacrylonitriles
Publisher URL http://pubs.rsc.org/en/Content/ArticleLanding/2014/TA/C4TA02521K#!divAbstract
Copyright Statement Copyright information regarding this work can be found at the following address: http://eprints.nottingh.../end_user_agreement.pdf
Additional Information : This document is CrossCheck deposited; : Supplementary Information; : The Royal Society of Chemistry has an exclusive publication licence for this journal; OPEN ACCESS: The accepted version of this article will be made freely available after a 12 month embargo period; : Received 20 May 2014; Accepted 21 August 2014; Advance Article published 28 October 2014; Version of Record published 4 November 2014

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