Porous macromolecular dihydropyridyl frameworks exhibiting catalytic and halochromic activity
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...
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| Format: | Article |
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Royal Society of Chemistry
2014
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| Online Access: | https://eprints.nottingham.ac.uk/29547/ |
| _version_ | 1848793808167239680 |
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| author | Xiao, Bo Easun, Timothy L. Dhakshinamoorthy, Amarajothi Cebula, Izabela Beton, Peter H. Titman, Jeremy J. Garcia, Hermenegildo Thomas, K. Mark Schröder, Martin |
| author_facet | Xiao, Bo Easun, Timothy L. Dhakshinamoorthy, Amarajothi Cebula, Izabela Beton, Peter H. Titman, Jeremy J. Garcia, Hermenegildo Thomas, K. Mark Schröder, Martin |
| author_sort | Xiao, Bo |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | 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. |
| first_indexed | 2025-11-14T19:06:11Z |
| format | Article |
| id | nottingham-29547 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T19:06:11Z |
| publishDate | 2014 |
| publisher | Royal Society of Chemistry |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-295472020-05-04T16:55:09Z https://eprints.nottingham.ac.uk/29547/ 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 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. Royal Society of Chemistry 2014-10-28 Article PeerReviewed Xiao, Bo, Easun, Timothy L., Dhakshinamoorthy, Amarajothi, Cebula, Izabela, Beton, Peter H., Titman, Jeremy J., Garcia, Hermenegildo, Thomas, K. Mark and Schröder, Martin (2014) Porous macromolecular dihydropyridyl frameworks exhibiting catalytic and halochromic activity. Journal of Materials Chemistry A, 2 . pp. 19889-19896. ISSN 2050-7488 porous macromolecular frameworks PMFs dialdehydes aminoacrylonitriles http://pubs.rsc.org/en/Content/ArticleLanding/2014/TA/C4TA02521K#!divAbstract doi:10.1039/c4ta02521k doi:10.1039/c4ta02521k |
| spellingShingle | porous macromolecular frameworks PMFs dialdehydes aminoacrylonitriles Xiao, Bo Easun, Timothy L. Dhakshinamoorthy, Amarajothi Cebula, Izabela Beton, Peter H. Titman, Jeremy J. Garcia, Hermenegildo Thomas, K. Mark Schröder, Martin Porous macromolecular dihydropyridyl frameworks exhibiting catalytic and halochromic activity |
| title | Porous macromolecular dihydropyridyl frameworks exhibiting catalytic and halochromic activity |
| title_full | Porous macromolecular dihydropyridyl frameworks exhibiting catalytic and halochromic activity |
| title_fullStr | Porous macromolecular dihydropyridyl frameworks exhibiting catalytic and halochromic activity |
| title_full_unstemmed | Porous macromolecular dihydropyridyl frameworks exhibiting catalytic and halochromic activity |
| title_short | Porous macromolecular dihydropyridyl frameworks exhibiting catalytic and halochromic activity |
| title_sort | porous macromolecular dihydropyridyl frameworks exhibiting catalytic and halochromic activity |
| topic | porous macromolecular frameworks PMFs dialdehydes aminoacrylonitriles |
| url | https://eprints.nottingham.ac.uk/29547/ https://eprints.nottingham.ac.uk/29547/ https://eprints.nottingham.ac.uk/29547/ |