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π-Extended dihydrophenazine based redox responsive polymers of intrinsic microporosity
Caterina Bezzu 
,
Beatrice Bartolomei ,
YUE WU,
Martina Vaccaro,
Mariagiulia Longo,
Maria Penelope De Santo,
Alessio Fuoco,
Maurizio Prato ,
Mariolino Carta ,
Jacopo Dosso
,
Beatrice Bartolomei ,
YUE WU,
Martina Vaccaro,
Mariagiulia Longo,
Maria Penelope De Santo,
Alessio Fuoco,
Maurizio Prato ,
Mariolino Carta ,
Jacopo Dosso
Journal of Materials Chemistry A
Swansea University Authors:
Caterina Bezzu , YUE WU, Mariolino Carta
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DOI (Published version): 10.1039/d5ta02477c
Abstract
Redox-switchable Polymers of Intrinsic Microporosity (PIMs) are a promising yet underexplored class of materials. Here, we introduce π-extended dihydrophenazine-based PIMs for gas separation. The tert-butyl substituted Phen-PIM-1 stands out as a rare example of a redox-active switchable polymer with...
| Published in: | Journal of Materials Chemistry A |
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| ISSN: | 2050-7488 2050-7496 |
| Published: |
Royal Society of Chemistry (RSC)
2025
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| Online Access: |
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| URI: | https://cronfa.swan.ac.uk/Record/cronfa69747 |
| Abstract: |
Redox-switchable Polymers of Intrinsic Microporosity (PIMs) are a promising yet underexplored class of materials. Here, we introduce π-extended dihydrophenazine-based PIMs for gas separation. The tert-butyl substituted Phen-PIM-1 stands out as a rare example of a redox-active switchable polymer with a high surface area (BET >600 m2 g−1) and excellent balance of porosity, pore size, and gas selectivity. Phen-PIM-1 is soluble in N-methyl pyrrolidone (NMP), enabling membrane fabrication, while the methyl-substituted Phen-PIM-2 is insoluble, highlighting the role of bulky tert-butyl groups (tBu) in solubility and film formation. Gas separation studies, performed on powder (IAST), demonstrate outstanding performance, with CO2/N2 selectivity up to 49. As a membrane material, Phen-PIM-1 shows competitive separation within the Robeson upper bound for several commercially important gas pairs, proving its potential for carbon capture and molecular sieving. Furthermore, these materials exhibit efficient and reversible redox switching upon chemical stimuli, leading to marked differences in properties and enhanced selectivity. This study establishes dihydrophenazine-based PIMs as a versatile platform for developing tunable, high-performance membranes for energy and environmental applications. |
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| College: |
Faculty of Science and Engineering |
| Funders: |
J. D. kindly acknowledges FRA2024-2025 funded by the University of Trieste and Microgrants 2024 funded by Regione FVG (LR 2/2011, ART. 4). M. P. is the AXA-Chair for Bionanotechnology (2016–2026). This work was supported by the University of Trieste, INSTM, the Italian Ministry of Education MIUR (cofin Prot. 20228YFRNL), and la Agencia Estatal de Investigaciones through grant PID2022-140419OB-I00 funded by MCIN/AEI/10.13039/501100011033. M. V. and A. F. received funding from the European Union's Horizon Europe research and innovation program under grant agreement no. 101115488, within the EIC pathfinder project “Double-Active Membranes for a sustainable CO2 – DAM4CO2” (HORIZON-EIC-2022-PATHFINDERCHALLENGES-01). C.G.B and M.C. gratefully acknowledge UK Research and Innovation (UKRI) under the UK government's Horizon Europe funding guarantee [grant number 10083164] associated with DAM4CO2. The authors gratefully acknowledge Daniel M. Dawson and the University of St Andrews for the 13C ssNMR service. |