Dibenzomethanopentacene‐Based Polymers of Intrinsic Microporosity for Use in Gas‐Separation Membranes

Gas Sepa a ion Dibenzome hanopen acene-Based Polyme s o In insic Mic opo osi y o Use in Gas-Sepa a ion Memb anes Jie Chen, Ma iagiulia Longo, Alessio Fuoco, Elisa Esposi o, Ma cello Mon eleone, Bibiana Comesaña Gánda a, Johannes Ca olus Jansen,* and Neil B. McKeown* Abs ac : Dibenzome hanopen acene (DBMP) is shown o be a use ul s uc u al componen o making Polyme s o In insic Mic opo osi y (PIMs) wi h p om- ise o making e icien memb anes o gas sepa a ions. DBMP-based monome s o PIMs a e eadily p epa ed using a Diels–Alde eac ion be ween 2,3-dime h- oxyan h acene and no bo nadiene as he key syn he ic s ep. Compa ed o da e o he a che ypal PIM-1, he inco po a ion o DBMP simul aneously enhances bo h gas pe meabili y and he ideal selec i i y o one gas o e ano he . Hence, bo h ideal and mixed gas pe me- abili y da a o DBMP- ich co-polyme s and an amidox- ime modi ied PIM a e close o he cu en Robeson uppe bounds, which de ine he s a e-o - he-a o he ade-o be ween pe meabili y and selec i i y, o se e al impo an gas pai s. Fu he mo e, long- e m s udies (o e �3 yea s) e eal ha he educ ion in gas pe meabili ies on ageing is less o DBMP-con aining PIMs ela i e o ha o o he high pe o ming PIMs, which is an a ac i e p ope y o he ab ica ion o memb anes o e icien gas sepa a ions. In oduc ion Polyme ic gas sepa a ion memb anes a e o inc easing use in indus y o oxygen o ni ogen en ichmen o ai (O2/N2), hyd ogen eco e y om ammonia pu ge gases (H2/N2) and na u al gas swee ening o biogas upg ading (CO2/CH4).[1] This is due o hei low ope a ing cos and ene gy consump ion ela i e o compe ing echnologies such as c yogenic dis illa ion. High pe o ming polyme s o he ab ica ion o gas sepa a ion memb anes should demon- s a e high pe meabili y (p oduc i i y) in combina ion wi h good selec i i y (pu i y o he p oduc s).[2] Howe e , poly- me ic memb anes su e om a well-known ade-o ela ionship be ween hei gas pe meabili y (PA) and selec i i y (PA/PB). This ade-o was i s quan i ied by Robeson in 1991 when iden i ying he uppe bounds o gas pai s in plo s o log(PA/PB) e sus log(PA), which p o ided a benchma k o polyme pe o mance a ha ime.[3] Sub- sequen ly, he posi ions o he gas pe meabili y da a o a new polyme ela i e o hese uppe bounds a e used as a uni e sal pe o mance indica o o e alua e i s po en ial pe o mance as a sepa a ion memb ane.[4] Polyme s o In insic Mic opo osi y (PIMs)[5] ha e eme ged as p omising ma e ials o gas sepa a ion memb anes.[6] In compa ison o mos o he classes o polyme , PIMs a e highly gas pe meable due o he ee olume c ea ed by he e icien packing o hei con o ed mac omolecula chains and a e easonably selec i i y due o hei igid used- ing s uc u es.[7] In 2008 gas pe meabili y da a o wo PIMs de i ed om a spi obisindane-based monome (PIM-1 and PIM-7) we e used o ede ine he Robeson uppe bounds o he pe meabili y/selec i i y ade-o ela ionship o he majo i y o gas pai s.[4a] Subsequen ly, new PIMs wi h imp o ed gas selec i i y we e de eloped by eplacing he ela i ely lexible spi obisindane uni wi h mo e igid s uc u al uni s such as spi obi luo ene,[8] e hanoan h acene,[9] ip ycene,[4b,8a,10] me hanopen acene[11] and T öge s base.[9a,12] In pa icula , da a om PIMs de i ed om ip ycene o benzo ip ycene componen s we e used o de ine new uppe bounds o O2/ N2, H2/N2and H2/CH4in 2015[4c] and, o he CO2/N2and CO2/CH4uppe bounds in 2019.[4b] These 2019 uppe bounds a e o ele ance o he pe o mance o po en ial memb anes o ca bon cap u e and o na u al gas/biogas upg ading, espec i ely. As pa o ou con inuing esea ch p og amme on iden i ying use ul igid s uc u al componen s o making PIMs, we iden i ied he po en ial o he 2:1 adduc om he Diels–Alde eac ion be ween an h acene and no bo na- diene (Scheme 1). The 1:1 an h acene/no bo nadiene ad- duc , i s epo ed in 1975,[13] is a well-s udied monome o he p epa a ion o high glass ansi ion empe a u e poly- me s using ing-opening-me a hesis-polyme isa ion (ROMP).[14] In con as , he 2:1 adduc , gi en he e he abb e ia ed name dibenzome hanopen acene (DBMP), was [*] D . J. Chen, D . B. Comesaña Gánda a, P o . N. B. McKeown EaS CHEM, School o Chemis y, Uni e si y o Edinbu gh Da id B ews e Road, Edinbu gh, EH9 3FJ (UK) E-mail: [email p o ec ed] D . M. Longo, D . A. Fuoco, D . E. Esposi o, D . M. Mon eleone, P o . J. Ca olus Jansen Ins i u e on Memb ane Technology, Na ional Resea ch Council o I aly (CNR-ITM) ia P. Bucci 17/C, 87036 Rende (CS) (I aly) E-mail: johannesca olus.jansen@cn .i © 2022 The Au ho s. Angewand e Chemie In e na ional Edi ion published by Wiley-VCH GmbH. This is an open access a icle unde he e ms o he C ea i e Commons A ibu ion Non-Comme cial License, which pe mi s use, dis ibu ion and ep oduc ion in any medium, p o ided he o iginal wo k is p ope ly ci ed and is no used o comme cial pu poses. Angewand e Chemie Resea ch A icles www.angewand e.o g How o ci e: Angew. Chem. In . Ed. 2023, 62, e202215250 In e na ional Edi ion: doi.o g/10.1002/anie.202215250 Ge man Edi ion: doi.o g/10.1002/ange.202215250 Angew. Chem. In . Ed. 2023,62, e202215250 (1 o 9) © 2022 The Au ho s. Angewand e Chemie In e na ional Edi ion published by Wiley-VCH GmbH epo ed only ecen ly.[15] I is wo h no ing an ea lie obse a ion o an uniden i ied “whi e solid”, which was emo ed om he c ude p oduc o he 1:1 adduc was almos ce ainly DBMP.[14a] The s uc u e o DBMP has se e al ea u es ha make i an a ac i e componen o making PIMs. Fo example, 1H NMR signals o he me h- ylene hyd ogens o DBMP a e ound a a highly shielded posi ion (δH=1.0 ppm) due o he p esence o he ing cu en o adjacen benzo uni s .[15] The e o e, his me h- ylene b idge is likely o ac as a wedge o ensu e s uc u al igidi y (Scheme 1). DBMP also possesses a la ge igid cle and o he ca i ies, ha p o ide in e molecula ee olume simila o hose o ip ycene,[16] which is he s uc u al uni o mos uppe bound pe o ming PIMs. In addi ion, i was an icipa ed ha DBMP-based p ecu so s o PIM could be p epa ed ela i ely simply om he Diels–Alde eac ion be ween an app op ia e an h acene de i a i e and no bo - nadiene. In con as , he la ge-scale syn hesis o ip ycene de i a i es can be di icul due o he equi ed gene a ion o he highly eac i e benzyne in e media e. Resul s and Discussion The a ge DBMP-based monome 1was designed o PIM syn hesis using he eac ion o i s wo ca echol eac i e uni s (i.e. 1,2-dihyd oxybenzene) wi h 2,3,5,6- e a luo o e eph- haloni ile (TFTPN) (Scheme 2). The equi ed p ecu so o monome 1is 2,3-dime hoxyan h acene, which was ob ained e icien ly om he F iedel–C a s acyla ion o ph halic anhyd ide wi h e a ole, ollowed by an acid-media ed cycliza ion and sodium bo ohyd ide educ ion o he an h aquinone in e media e.[17] The Diels–Alde eac ion be ween an excess o 2,3-dime hoxyan h acene and no bo - nadiene p oduces a c ude p oduc ha is composed o h ee DBMP egioisome s (Scheme 2: 2a,2b and 2c)— wo o which possess all ou o he me hoxy g oups on he same side o he molecule (2b and 2c) and a single isome 2a wi h he me hoxy g oups on opposi e sides o he DBMP uni . Isome s 2b and 2c we e deemed as undesi able as PIM p ecu so s because a p e ious s udy indica ed ha simila monome s eac o o m small cyclic oligome s a he han high molecula mass PIMs.[18] Con enien ly, he desi ed DBMP isome 2a was o med in g ea e yield (33%) and was elu ed i s du ing sepa a ion by column ch oma og- aphy. Isome 2a could be eadily iden i ied using 1H NMR Scheme 1. The 1:1 and 2:1 (DBMP) adduc s o med by he Diels–Alde eac ion be ween an h acene and no bo nadiene. P oduc o ma ion is con olled by he a io o p ecu so s. Scheme 2. The syn hesis o DBMP monome 2a and he se ies o polyme s p epa ed om i . Reagen s and condi ions: i. xylene, 260°C, 96 h; ii. BB 3, DCM, RT, 3 h; iii. 2,3,5,6- e a luo o e eph haloni ile and 5,5’,6,6’- e ahyd oxy-3,3,3’,3’- e ame hyl-spi obisindane, K2CO3, 65°C, 72 h; i . NH2OH, NMP, 65°C, 72 h. Angewand e Chemie Resea ch A icles Angew. Chem. In . Ed. 2023,62, e202215250 (2 o 9) © 2022 The Au ho s. Angewand e Chemie In e na ional Edi ion published by Wiley-VCH GmbH 15213773, 2023, 8, Downloaded om h ps://onlinelib a y.wiley.com/doi/10.1002/anie.202215250 by Readcube (Lab i a Inc.), Wiley Online Lib a y on [26/01/2024]. See he Te ms and Condi ions (h ps://onlinelib a y.wiley.com/ e ms-and-condi ions) on Wiley Online Lib a y o ules o use; OA a icles a e go e ned by he applicable C ea i e Commons License spec oscopy due o he non-equi alence o he highly shielded me hylene hyd ogens (δH=0.93 and 1.00 ppm) and he la ge geminal coupling be ween hem (JHH =11 Hz) (Figu e S1). P ecu so 2a was ans o med o he equi ed bisca echol monome 1by a simple deme hyla ion eac ion using BB 3(Scheme 2). Full syn he ic de ails a e p o ided in he Suppo ing In o ma ion. Ini ially a polyme , deno ed as PIM-DBMP, was p e- pa ed om monome 1and 2,3,5,6- e a luo o e eph haloni- ile (TFTPN) using he well-es ablished polyme isa ion based on he o ma ion o benzodioxin linkages ha has o en been used o PIMs syn hesis.[5,19] Un o una ely, PIM- DBMP p o ed insoluble in mos o ganic sol en s and only pa ially soluble in quinoline, hence i was di icul o cha ac e ise, ne e heless, he solid s a e 13C NMR spec um o PIM-DBMP is consis en wi h i s s uc u e (Figu e S2). The e o e, in o de o in es iga e he e ec o DBMP inco po a ion on PIM p ope ies, co-polyme s deno ed as PIM-DBMPxwe e p epa ed using mola a ios o x=0.1, 0.25, 0.5, 0.75 and 0.9 o DBMP monome 1 ela i e o 5,5’,6,6’- e ahyd oxy-3,3,3’,3’- e ame hylspi obisindane (SBI) (i.e. he monome used o he syn hesis o PIM-1, Scheme 2).[5] In addi ion, modi ica ion o he ni ile g oups o PIM-DBMP o amidoxime (AO) subs i uen s,[20] o gi e PIM-DBMP-AO, ia eac ion wi h hyd oxylamine (Scheme 2), p o ided solubili y in he pola ap o ic sol en N-me hyl-2-py olidone (NMP). I was ecen ly epo ed ha PIM-DBMP-AO shows p omise as an ionic anspo memb ane o edox low ba e ies.[21] De ails o he physical p ope ies o each polyme a e p o ided in Table 1. The copolyme PIM-DBMP0.75 was only soluble in quinoline. In con as , copolyme s PIM-DBMP0.5, PIM-DBMP0.25 and PIM-DBMP0.1 all ha e good solubili y in CHCl3allowing analysis using gel pe mea ion ch oma og- aphy (GPC), which indica ed ha hese polyme s possess high molecula mass. Solubili y in CHCl3also acili a ed cha ac e isa ion by 1H NMR, which con i med ha he a io o he inco po a ed DBMP componen was consis en wi h he mola a io o monome s used o syn hesis (Fig- u e S3).The amoun o DBMP uni in each o he copoly- me s could also be es ima ed om he mal g a ime ic analysis (TGA) wi h each DBMP-con aining polyme show- ing commensu a e weigh loss a an onse empe a u e o 360°C due o he elease o no bo nadiene h ough a e e se Diels–Alde eac ion (Figu e S4). Al hough he small quan- i y p oduced o each polyme (�1 g ) was insu icien o a ull analysis o mechanical p ope ies, a omic o ce mic o- scopy (AFM) demons a ed ha he Young’s modulus inc eased wi h g ea e amoun s o he mo e igid DBMP componen (Table 1 and Figu e S5).[22] Fo all DBMP con aining polyme s, he N2adso p ion iso he ms ob ained a 77 K show high N2up akes a low ela i e p essu es (p/p0<0.1 ba ) (Figu e S6), indica i e o in insic mic opo osi y. Appa en BET su ace a eas (SABET) o all copolyme s in hei powde o m a e in he ange o 730–830 m2g1simila o ha o PIM-1, o which li e a u e alues a e in he ange 740–900 m2g1(Table 1). The shape o each adso p ion iso he m is simila o ha o PIM-1, wi h dis inc hys e esis be ween adso p ion and deso p ion, which can be a ibu ed o swelling o he polyme du ing N2up ake (Figu e S6). All DBMP-con ain- ing polyme s show signi ican ly la ge CO2up ake a 1 ba and 273 K (2.4–2.6 mmolg1) han PIM-1 (2.0 mmolg1) (Table 1, Figu e S7), indica ing a g ea e concen a ion o ul amic opo es (<0.7 nm). Howe e , he e is no clea end o inc easing CO2up ake o g ea e inco po a ion o DBMP. The modi ied polyme PIM-DBMP-AO demon- s a es bo h g ea e SABET and CO2up ake a 1 ba and/ 273 K han he equi alen PIM-1-AO (Table 1, Fig- u e S7).[20,23] The N2iso he m o PIM-DBMP-AO (Fig- u e S6) demons a es a ela i ely small deg ee o hys e esis be ween adso p ion and deso p ion, simila o ha seen o iso he ms o PIM-1-AO, which is consis en wi h educed swelling due o g ea e in e -chain cohesion om hyd ogen- bonding. Flexible and de ec - ee sel -s anding memb anes o PIM-DBMP0.1, PIM-DBMP0.25, PIM-DBMP0.5 we e p epa ed by cas ing hei CHCl3solu ions, whe eas PIM-DBMP0.75 was cas om i s quinoline solu ion (Figu e S8). PIM- DBMP0.9 and PIM-DBMP ga e b i le ilms om quinoline, in which hey a e only pa ially soluble, howe e , a obus ilm o nea PIM-DBMP-AO could be p epa ed om NMP Table 1: Physical p ope ies o DBMP con aining polyme s wi h da a o PIM-1 and PIM-1-AO included o compa ison. Polyme Mw [gmol1] Mw/MnSABET[a] [m2g1] CO2up ake[b] [mmolg1] VTo al[c] [mLg1] Young’s Modulus[d] [MPa] Solubili y PIM-1 – – 740–900 2.0 0.57 1250 CHCl3 PIM-DBMP0.1 125000[e] 2.1 801 2.5 0.66 2400 CHCl3 PIM-DBMP0.25 71000[e] 1.7 760 2.4 0.62 2550 CHCl3 PIM-DBMP0.5 65000[e] 2.3 830 2.6 0.67 2870 CHCl3 PIM-DBMP0.75 –[ ] –[ ] 728 2.4 0.54 3150 Quinoline PIM-DBMP0.9 –[ ] –[ ] 817 2.4 0.73 – Quinoline[g] PIM-DBMP –[ ] –[ ] 790 2.4 0.73 – Quinoline[g] PIM-DBMP-AO –[ ] –[ ] 645 3.1 0.38 – NMP PIM-1-AO –[ ] –[ ] 482[20] 2.7[20] 0.27[20] – DMSO, NMP [a] BET su ace a ea (SABET) calcula ed om N2adso p ion iso he m ob ained a 77 K. [b] CO2up akes a 1 ba and 273 K. [c] To al ee olume (VTo al) es ima ed om N2adso p ion a p/p0=0.98. [d] Young’s modulus o memb anes measu ed by a omic o ce mic oscopy (AFM). [e] F om GPC analysis ela i e o polys y ene s anda ds. [ ] No measu ed due o insolubili y in an app op ia e sol en o GPC. [g] Pa ially soluble in quinoline. Angewand e Chemie Resea ch A icles Angew. Chem. In . Ed. 2023,62, e202215250 (3 o 9) © 2022 The Au ho s. Angewand e Chemie In e na ional Edi ion published by Wiley-VCH GmbH 15213773, 2023, 8, Downloaded om h ps://onlinelib a y.wiley.com/doi/10.1002/anie.202215250 by Readcube (Lab i a Inc.), Wiley Online Lib a y on [26/01/2024]. See he Te ms and Condi ions (h ps://onlinelib a y.wiley.com/ e ms-and-condi ions) on Wiley Online Lib a y o ules o use; OA a icles a e go e ned by he applicable C ea i e Commons License solu ion. Each ilm, wi h a hickness be ween 88–125 μm, was ea ed wi h me hanol o emo e he esidual cas ing sol en and e e se he e ec s o physical ageing p io o gas pe meabili y measu emen s.[6] The pu e gas pe meabili y o each ilm was measu ed ini ially wi hin a day o me hanol ea men , hen a e mode a e ageing (33–140 days) and inally a e long- e m ageing (>2.5 yea s). The gas pe meabili y coe icien s and ideal gas selec i i ies o he no el polyme s, oge he wi h hose o PIM-1 and PIM-1-AO o compa ison, a e p o ided in Table 2. Da a poin s a e placed on Robeson plo s o CO2/CH4, CO2/N2, O2/N2, H2/N2, H2/CH4and He/N2(Fig- u e 1a– ). In di ec compa ison wi h he equi alen da a o PIM- 1,[8b,c] i is appa en ha e en he ela i ely small amoun o DBMP wi hin PIM-DBMP0.1 enhances signi ican ly bo h gas pe meabili y and selec i i y. The ideal selec i i y ends o inc ease u he wi h inc easing amoun o he igid DBMP uni and is highes o PIM-DBMP0.75. In line wi h he usual beha iou o PIMs, ageing o he ilms educes pe meabili y and imp o es selec i i y. This esul s in da a o aged ilms being placed well abo e he 2008 Robeson uppe bounds. Da a o PIM-DBMP0.75 and PIM-DBMP-AO lie close o, o in some cases sligh ly abo e, he la es uppe bounds (Figu e 1). The o igin o he selec i i y enhancemen om he inco po a ion o he DBMP uni and he AO g oup was in es iga ed by he analysis o gas di usion coe icien s (DA, Table S1) and solubili y coe icien s (SA, Table S2) ob ained om he ime-lag da a du ing gas pe meabili y measu e- men s. Gas anspo h ough a polyme is desc ibed by he solu ion-di usion model wi h PA=DA×SA, so ha selec i - Table 2: Memb ane Thickness (l, μm), gas pe meabili ies (PA, Ba e ; 1 Ba e =1010 cm3STP cmcm2s1cmHg1) and ideal selec i i ies (PA/PB) o eshly me hanol ea ed and aged ilms measu ed a 25°C and 1 ba o eed p essu e. Polyme l[μm] Pe meabili y (Ba e ) Selec i i y N2O2CO2CH4H2He CO2/CH4CO2/N2O2/N2H2/N2H2/CH4He/N2 PIM-1[8b] 128 823 2270 13600 1360 5010 1950 10.0 16.5 2.8 6.1 3.7 2.4 (1200 days)[8c] 110 125 600 2840 159 2400 1140 17.9 22.7 4.8 19.2 15.1 9.1 PIM-DBMP0.1 81 1000 3310 18900 1620 7810 2960 11.7 18.9 3.3 7.8 4.8 3.0 (33 days) 81 506 2120 10700 688 6460 2580 15.5 21.1 4.2 12.8 9.4 5.1 (140 days) 81 403 1780 8500 517 5860 2430 16.4 21.1 4.4 14.5 11.3 6.0 (1154 days)[a] 102 390 1580 7900 488 4560 1860 16.2 20.3 4.1 11.7 9.4 4.8 PIM-DBMP0.25 127 1180 3880 21600 1930 8880 3270 11.2 18.3 3.3 7.5 4.6 2.8 (34 days) 127 652 2680 13200 884 7620 2940 14.9 20.2 4.1 11.7 8.6 4.5 (134 days) 127 639 2530 12200 811 6960 2690 15.0 19.0 4.0 10.9 8.6 4.2 (1156 days)[a] 121 455 1960 9680 569 5710 2230 17.0 21.3 4.3 12.6 10.3 4.9 PIM-DBMP0.5 125 1210 4080 22200 1840 8970 3150 12.1 18.3 3.4 7.4 4.9 2.6 (118 days) 125 501 2320 11980 630 7230 2720 19.0 24.0 4.6 14.4 11.5 5.4 (1133 days) 125 503 2380 11000 637 7290 2850 17.3 22.0 4.7 14.5 11.4 5.7 (1276 days) 125 400 1970 9120 479 6680 2580 19.1 22.8 4.9 16.7 14.0 6.5 (1394 days)[b] 125 408 2126 9573 459 7784 3041 20.9 23.5 5.2 19.1 17.0 7.5 PIM-DBMP0.75 88 827 3390 20300 1500 9530 3350 13.5 24.6 4.1 11.5 6.3 4.1 (55 days) 88 386 2130 10500 528 7920 3080 20.0 27.4 5.5 20.5 15.0 8.0 (880 days) 88 316 1640 7560 381 6660 2680 19.8 23.9 5.2 21.0 17.5 8.5 (1022 days) 88 239 1340 5970 278 5820 2400 21.5 25.0 5.6 24.4 21.0 10.0 PIM-DBMP-AO 89 106 691 3520 106 4530 1720 33.2 33.2 6.5 42.7 42.7 16.2 (70 days) 89 84 561 2910 93 3810 1420 31.4 34.6 6.7 45.1 41.1 16.8 (1011 days) 89 72 415 2260 82 2670 1080 27.6 31.2 5.7 37.0 32.6 15.0 (1152 days) 89 77 458 2290 83 2710 1070 27.6 29.7 6.0 35.1 32.6 13.8 (1267 days)[b] 89 42 262 1353 40 1839 758 33.7 32.5 6.3 44.1 45.8 18.2 PIM-1-AO[23] 90 33 147 1150 34 912 412 34.0 33.0 4.5 27.6 26.8 12.5 PIM-1-AO[24] 40 18 75.0 625 21.5 417 218 29.0 34.7 4.2 23.2 19.4 12.1 [a] Second memb ane o he same polyme ba ch. [b] Sample es ed a e he mixed gas pe meabili y measu emen s. Angewand e Chemie Resea ch A icles Angew. Chem. In . Ed. 2023,62, e202215250 (4 o 9) © 2022 The Au ho s. Angewand e Chemie In e na ional Edi ion published by Wiley-VCH GmbH 15213773, 2023, 8, Downloaded om h ps://onlinelib a y.wiley.com/doi/10.1002/anie.202215250 by Readcube (Lab i a Inc.), Wiley Online Lib a y on [26/01/2024]. See he Te ms and Condi ions (h ps://onlinelib a y.wiley.com/ e ms-and-condi ions) on Wiley Online Lib a y o ules o use; OA a icles a e go e ned by he applicable C ea i e Commons License Figu e 1. Robeson plo s o he a) CO2/CH4, b) CO2/N2, c) O2/N2, d) H2/N2, e) H2/CH4and ) He/N2gas pai s showing he posi ion o he gas pe meabili y and ideal selec i i y da a o ilms o PIM-DBMP0.1 (*,~,■,♦), PIM-DBMP0.25 (*,~,■,♦), PIM-DBMP0.5 (*,~,■,♦,x), PIM-DBMP0.75 (*,~,■,♦), PIM-DBMP-AO (*,~,■,♦,x). All da a a e measu ed a 25°C unless s a ed o he wise, and eshly MeOH ea ed samples a e indica ed as ci cles (*) and u he aging is indica ed in he o de ~<&<^<x, whe e aged samples es ed a e he mix u es a e indica ed as (x,x). Repo ed da a om equi alen ilms o PIM-1[8b,c] (*,■) and PIM-1-AO[23] (x) a e shown o compa ison. The g oups o open symbols in he Robeson plo s o CO2/CH4and CO2/N2 ep esen he mixed gas pe meabili y da a om Figu e 3 o PIM-DBMP0.5 (*,~) and PIM-DBMP-AO (*,~). The uppe bounds a e ep esen ed by blue lines (1991), ed lines (2008), yellow lines o O2/N2, H2/N2and H2/CH4(2015), pu ple lines o CO2/N2and CO2/CH4(2019), and a dashed line o CO2/CH4mix u es (2018). Angewand e Chemie Resea ch A icles Angew. Chem. In . Ed. 2023,62, e202215250 (5 o 9) © 2022 The Au ho s. Angewand e Chemie In e na ional Edi ion published by Wiley-VCH GmbH 15213773, 2023, 8, Downloaded om h ps://onlinelib a y.wiley.com/doi/10.1002/anie.202215250 by Readcube (Lab i a Inc.), Wiley Online Lib a y on [26/01/2024]. See he Te ms and Condi ions (h ps://onlinelib a y.wiley.com/ e ms-and-condi ions) on Wiley Online Lib a y o ules o use; OA a icles a e go e ned by he applicable C ea i e Commons License i y (PA/PB) o a polyme is he p oduc o di usi i y selec i i y (DA/DB) and solubili y selec i i y (SA/SB).[25] The o de o dec easing di usi i y is He>H2>O2>CO2>N2> CH4as de e mined by he e ec i e diame e , de ,[26] o he gas molecule. I has been es ablished ha he s eepness o he slope o he co ela ion be ween DAand he squa e o gas e ec i e diame e o O2, CO2, N2and CH4is a good indica o o he di usi i y selec i i y o a polyme (Fig- u e 2).[26] Fo PIMs his slope is cha ac e is ically di e en o he small molecules He and H2, as epo ed p e iously.[27] Clea ly, he He and H2di usi i y is signi ican ly highe in all copolyme s han in PIM-1, mos likely due o a mo e in e connec ed ee olume ne wo k in he copolyme s. The slope o D s. d2 e is s eepe o he PIM copolyme PIM- DBMP0.75 con aining he highes a io o DBMP o SBI uni s and is e en g ea e o PIM-DBMP-AO. This enhanced molecula sie ing is a ibu able o he g ea e igidi y o he DBMP uni ela i e o ha o he SBI uni . These alues o di usion selec i i y a e simila o hose obse ed o he uppe bound-de ining ip ycene-based PIMs and a ise om he es ic ed anspo o a la ge gas molecule h ough he igid polyme ma ix.[4b] T anspo o la ge gas molecules in ol es a hopping mechanism om one elemen o ee olume o ano he and equi es g ea e he mal ene gy o he necessa y opening o occu ia ib a ions o he igid polyme .[4b,25, 27] Inc easing di usion selec i i y on aging is he main cause o he enhanced ideal gas selec i i y and his can be a ibu ed o p e e en ial loss o la ge ee olume elemen s (>0.7 nm) o e hose o smalle diame e . Gene ally, he gas solubili ies a e high, a common ea u e o all PIMs, and he pa icula ly high alues o CO2 solubili y, ollowed by hose o CH4(Table S2), a e e lec ed in he o de o dec easing gas pe meabili ies being CO2> H2>O2>He>CH4>N2 o all he PIM-DBMP copolyme s. In mos cases, he solubili y selec i i y emains cons an as he a io o DBMP o SBI uni s inc eases and as he ilms age. The excep ionally high alues o SCO2a e ela ed o he amoun o ee olume p esen in he polyme (i.e. in insic mic opo osi y). The e o e, i s loss du ing p olonged aging causes a dec ease in SCO2. Fo he CO2/N2gas pai , he high pe mselec i i y is p edominan ly due o he la ge di e ence in solubili y, and PCO2/PN2is hus p opo ional o SCO2/SN2 wi h DCO2/DN2being close o uni y (Table S1). The e o e, ageing o he ilms p o ides a lowe con ibu ion o solubili y o he o e all ideal selec i i y (PCO2/PN2). This is especially he case o PIMs wi h high DBMP con en , whe e long- e m ageing signi ican ly educes PCO2/PN2. Simila ageing beha iou has been obse ed o o he PIMs based on igid s uc u al uni s.[8c] Fo PIM-DBMP-AO, he ini ial gas pe meabili y is much lowe bu he ideal selec i i y is highe wi h espec o he o he DBMP-based PIMs. This can be explained by he polyme possessing a much dense ini ial s a e a e me h- anol ea men , induced by he g ea e in e -chain cohesion due o ex ensi e hyd ogen bonding be ween he amidoxime g oups.[23] This leads o slowe gas di usion bu mo e p onounced size-sie ing p ope ies, highligh ed by he much s eepe slope in Figu e 2. Physical ageing is a gene al ea u e o glassy polyme s, in which he polyme de elops a mo e igh ly packed s a e leading o a educ ion in gas pe meabili y. Fo high ee olume polyme s such as PIMs he pe meabili y educ ion can be e y la ge. Ex ended s udies (>1000 days) we e conduc ed on he ilms o in es iga e he impac o he DBMP uni on gas pe meabili y (Table 2). O e all, he gas pe meabili y educ ion o he DBMP copolyme ilms is in he ange 36–50%, which is signi ican ly less han ha o a simila ilm o PIM-1 (74%) and a simila ly deep-aged ilm o a spi obi luo ene-based PIM (PIM-SBF-1; 66%).[8c] This sugges s ha he inco po a ion o DBMP uni s signi ican ly slows physical ageing o he ilms. Long- e m ageing o he PIM-DBMP-AO ilm esul s in only a small o e all educ- ion in gas pe meabili ies bu , unusually, he loss o pe meabili y is g ea e o smalle gas molecules (He and H2) due o a signi ican educ ion o hei di usi i y (Fig- u e S9). This esul s in a ela i ely small dec ease in selec i i y, which is likely o be associa ed wi h loss o small elemen s o ee olume (<0.7 nm). This unusual ageing beha iou appea s o be ela ed o he AO modi ica ion and his should be in es iga ed o o he AO-modi ied PIMs. Ne e heless, da a o he long- e m aged ilm o PIM- DBMP-AO a e s ill imp essi e (e.g. PO2=262 Ba e ; PO2/ PN2=6.3) especially in compa ison wi h hose o PIM-1-AO. Based on he pu e gas pe meabili ies and ideal selec i - i ies, we en isage he po en ial applica ion o hese mem- b anes in biogas upg ading o in CO2cap u e om lue gas. The mixed gas pe meabili y was he e o e measu ed up o 6 ba wi h mix u es o CO2/CH4(35/65 ol%) and CO2/N2 (15/85 ol%), ep esen a i e o biogas and CO2 ich lue gas, espec i ely, using ou p e iously epo ed cus omized se up.[28] Unde much ha she condi ions, wi h high p es- Figu e 2. Co ela ion o di usi i y coe icien (DA) wi h he squa ed e ec i e gas diame e (d2e ) o gas molecule (He=1.78, H2=2.14, O2=2.89, CO2=3.02, N2=3.04, CH4=3.18 Å)[26] o eshly me hanol ea ed ilms o PIM-DBMP0.1 (*), PIM-DBMP0.25 (*), PIM-DBMP0.5 (*), PIM-DBMP0.75 (*), PIM-DBMP-AO (*), and PIM-1 (*). Angewand e Chemie Resea ch A icles Angew. Chem. In . Ed. 2023,62, e202215250 (6 o 9) © 2022 The Au ho s. Angewand e Chemie In e na ional Edi ion published by Wiley-VCH GmbH 15213773, 2023, 8, Downloaded om h ps://onlinelib a y.wiley.com/doi/10.1002/anie.202215250 by Readcube (Lab i a Inc.), Wiley Online Lib a y on [26/01/2024]. See he Te ms and Condi ions (h ps://onlinelib a y.wiley.com/ e ms-and-condi ions) on Wiley Online Lib a y o ules o use; OA a icles a e go e ned by he applicable C ea i e Commons License su es and CO2 ich gas s eams, PIMs a e known o be subjec no only o physical aging, as al eady discussed abo e o he single gases, bu also o plas iciza ion.[29] Weake e ec s we e also obse ed in his wo k, whe e PIM- DBMP-AO shows a sligh hys e esis be ween he p essu e- inc ease s eps and he subsequen p essu e-dec ease s eps o CO2/CH4(Figu e 3a) and CO2/N2mix u es (Figu e 3c), in bo h cases wi h an inc ease in pe meabili y du ing dep essu iza ion, and only o CO2/CH4a sligh loss in selec i i y. This sugges s a weak dila ion o he memb ane upon exposu e o he highe CO2pa ial p essu es (concen- a ions), which is no eco e ed on he ime scale o he measu emen s, due o he slow chain dynamics o he e y igid ladde polyme s. Ins ead, PIM-DBMP0.5 only shows hys e esis o he CO2/CH4mix u e (Figu e 3b), bu in his case he CO2pe meabili y sligh ly inc eases and he CH4 pe meabili y dec eases, esul ing in a somewha highe selec i i y a e exposu e o he highe CO2pa ial p es- su es. This sugges s a simul aneous dila ion ( a ou ing CO2 pe mea ion) and physical aging (a ec ing nega i ely espe- cially he la ge CH4molecules), p obably esul ing in a na owing o he bo le necks be ween he ee olume elemen s.[27] In all cases, he CO2pe meabili y ends o dec ease wi h inc easing p essu e o he CO2/CH4(35/65 ol%) mix u e and he CO2/N2(15/85 ol%) mix u e, as al eady obse ed unde simila condi ions o o he PIMs, such as PIM-2,[30] bu his dec ease is much s onge in PIM-DBMP0.5 han in PIM-DBMP-AO. Especially o he CO2/CH4mix u e, i also leads o a modes dec ease in he selec i i y, whe eas o he CO2/N2(15/85 ol%) mix u e he dec ease in selec i i y is only obse ed in PIM-DBMP0.5. The dec ease Figu e 3. Mixed gas pe meabili y o CO2(*,&) CH4, (♦,^) N2(*,&) and selec i i y o CO2/CH4(35/65 Vol%; ♦,^) and CO2/N2(15/85 Vol%; ~,~) mix u es in PIM-DBMP-AO (a, c) and PIM-DBMP0.5 (b, d). Solid symbols ep esen he inc easing p essu e s eps and open symbols he subsequen dec easing p essu e s eps. Single gas pe meabili ies a 1 ba in he mixed gas se up (&), a e shown o compa ison and show he nea ly pe ec o e lap wi h he mixed gas pe mea ion da a on he same se up. Single gas pe meabili ies a 1 ba in he ixed olume ime lag se up a e also epo ed o compa ison be ween he wo me hods (x). Lines a e plo ed as a guide o he eye and he a ows poin owa ds he axis whe e o ead he da a. The maximum s age cu is CO2<1.5%, N2<0.65% and CH4<0.65% in PIM-DBMP0.5, and CO2<0.45%, N2<0.01% and CH4<0.008% in PIM-DBMP-AO. Angewand e Chemie Resea ch A icles Angew. Chem. In . Ed. 2023,62, e202215250 (7 o 9) © 2022 The Au ho s. Angewand e Chemie In e na ional Edi ion published by Wiley-VCH GmbH 15213773, 2023, 8, Downloaded om h ps://onlinelib a y.wiley.com/doi/10.1002/anie.202215250 by Readcube (Lab i a Inc.), Wiley Online Lib a y on [26/01/2024]. See he Te ms and Condi ions (h ps://onlinelib a y.wiley.com/ e ms-and-condi ions) on Wiley Online Lib a y o ules o use; OA a icles a e go e ned by he applicable C ea i e Commons License in pe meabili y is a ypical consequence o he dual mode so p ion mechanism, while a highe p essu es han hose used in his wo k, plas iciza ion may lead o mo e complex phenomena, such as an inc ease o CO2pe meabili y wi h p essu e and a subsequen dec ease wi h ime[31] and usually a educ ion o he mixed gas selec i i y a highe p essu es,[1c] al hough an inc ease in selec i i y has also been obse ed o PIMs wi h pa icula ly a ou able compe i i e so p ion.[32] The mixed gas pe meabili y da a o PIM- DBMP0.5 a e simila o ha ob ained om single gas measu emen s and close o he p oposed 2019 CO2/CH4and CO2/N2uppe bounds (Figu e 1a and b). PIM-DBMP-AO also exhibi s a p omising pe o mance in mixed gas meas- u emen s, loca ing a abo e he 2018 CO2/CH4uppe bound o mixed gas[1c] (Figu e 1a). Fo compa ison, he single gas pe mea ion measu emen s, de e mined on he same c oss- low appa a us (Figu e 3, &), show mino di e ences wi h he mixed gas pe mea ion measu emen s. Ins ead, he measu emen s on he ixed olume ime lag appa a us (Figu e 3, ×) a e sys ema ically lowe in bo h polyme s, especially o CO2(10–20%), esul ing in a sligh ly lowe ideal selec i i y as well. This is mos likely due o he di e en measu emen p inciple in he wo ins umen s, bu may in pa also be a esul o he sample his o y, since measu emen s in he ixed olume se up we e done a e he en i e cycle wi h he gas mix u es. Conclusion The ecen ly epo ed DBMP uni is shown o be a use ul s uc u al componen o making PIMs ha show p omise o he ab ica ion o gas sepa a ion memb anes. Syn hesis o he key DBMP monome 1is ela i ely s aigh o wa d and could be mo e easily ca ied ou on a la ge scale ela i e o ha o ip ycene based monome s ha p o ide high pe o mance PIMs. Despi e he lack o solubili y o he homopolyme PIM-DBMP in o ganic sol en s, he amidox- ime modi ied de i a i e (PIM-DBMP-AO) p o ed soluble in NMP om which obus ilms could be cas . Inco po- a ion o he DBMP uni in o andom copolyme s wi h SBI uni s also p o ided samples ha could be cas as ilms om chlo o o m solu ion. These ilms show ha DBMP inco po- a ion enhances bo h pe meabili y and selec i i y ela i e o PIM-1 and sugges s ha DBMP has a simila bene icial e ec on pe o mance as ip ycene o benzo ip ycene as a s uc u al uni . F om a p ac ical pe spec i e, he co-polyme PIM-DBMP0.5 p o ides an excellen comp omise be ween pe o mance (i.e. nea o he uppe bound o se e al gas pai s) and ease o p ocessabili y (i.e. eely soluble in chlo o o m). PIM-DBMP0.50 would also be mo e cos - e ec i e due o he use o he inexpensi e SBI co-monome in i s syn hesis. The memb anes main ain mos o hei excellen pe o mance unde mixed gas pe mea ion con- di ions wi h CO2/CH4and CO2/N2mix u es, opening in e - es ing pe spec i es in biogas upg ading and ca bon cap u e om CO2 ich lue gas. Acknowledgemen s P o . M. P. De San o (Uni e si y o Calab ia) is g a e ully acknowledged o help wi h he AFM o ce spec oscopy measu emen s. The p ojec is pa ially sponso ed by he Depa men o he De ence Th ea Reduc ion Agency g an numbe HDTRA1-18-1-0054. Con lic o In e es The au ho s decla e no con lic o in e es . Da a A ailabili y S a emen The da a ha suppo he indings o his s udy a e a ailable in he Suppo ing In o ma ion o his a icle. Keywo ds: Ageing ·Dibenzome hanopen acene ·Gas Sepa a ion ·Memb anes ·Polyme s o In insic Mic opo osi y [1] a) S. Wang, X. Li, H. Wu, Z. Tian, Q. Xin, G. He, D. Peng, S. Chen, Y. Yin, Z. Jiang, M. D. Gui e , Ene gy En i on. Sci. 2016,9, 1863–1890; b) D. S. Sholl, R. P. Li ely, Na u e 2016, 532, 435–437; c) Y. Wang, X. Ma, B. S. Ghanem, F. Alghunai- mi, I. Pinnau, Y. Han, Ma e . Today Nano 2018,3, 69–95; d) Y. Yampolskii, Mac omolecules 2012,45, 3298–3311; e) E. Esposi- o, L. Dellamuzia, U. Mo e i, A. Fuoco, L. Gio no, J. C. Jansen, Ene gy En i on. Sci. 2019,12, 281–289. [2] a) P. M. Budd, N. B. McKeown, Polym. Chem. 2010,1, 63–68; b) S. Kim, Y. M. Lee, P og. Polym. Sci. 2015,43, 1–32; c) A. F. Bushell, P. M. Budd, M. P. A ield, J. T. A. Jones, T. Hasell, A. I. Coope , P. Be na do, F. Bazza elli, G. Cla izia, J. C. Jansen, Angew. Chem. In . Ed. 2013,52, 1253–1256; Angew. Chem. 2013,125, 1291–1294. [3] a) L. M. Robeson, J. Memb . Sci. 1991,62, 165–185; b) B. D. F eeman, Mac omolecules 1999,32, 375–380. [4] a) L. M. Robeson, J. Memb . Sci. 2008,320, 390–400; b) B. Comesaña-Gánda a, J. Chen, C. G. Bezzu, M. Ca a, I. Rose, M.-C. Fe a i, E. Esposi o, A. Fuoco, J. C. Jansen, N. B. McKeown, Ene gy En i on. Sci. 2019,12, 2733–2740; c) R. Swaidan, B. Ghanem, I. Pinnau, ACS Mac o Le . 2015,4, 947– 951. [5] P. M. Budd, B. S. Ghanem, S. Makhseed, N. B. McKeown, K. J. Msayib, C. E. Ta e shall, Chem. Commun. 2004, 230–231. [6] N. B. McKeown, Polyme 2020,202, 122736. [7] a) N. B. McKeown, Cu . Opin. Chem. Eng. 2022,36, 100785; b) Y. Wang, B. S. Ghanem, Y. Han, I. Pinnau, Cu . Opin. Chem. Eng. 2022,35, 100755; c) X. Chen, L. Wu, H. Yang, Y. Qin, X. Ma, N. Li, Angew. Chem. In . Ed. 2021,60, 17875– 17880; Angew. Chem. 2021,133, 18019–18024. [8] a) C. G. Bezzu, A. Fuoco, E. Esposi o, M. Mon eleone, M. Longo, J. C. Jansen, G. S. Nichol, N. B. McKeown, Ad . Func . Ma e . 2021,31, 2104474; b) C. G. Bezzu, M. Ca a, A. Tonkins, J. C. Jansen, P. Be na do, F. Bazza elli, N. B. McKeown, Ad . Ma e . 2012,24, 5930–5933; c) C. G. Bezzu, M. Ca a, M. C. Fe a i, J. C. Jansen, M. Mon eleone, E. Esposi o, A. Fuoco, K. Ha , T. P. Liyana-A achchi, C. M. Colina, N. B. McKeown, J. Ma e . Chem. A 2018,6, 10507–10514. [9] a) M. Ca a, R. Malpass-E ans, M. C oad, Y. Rogan, J. C. Jansen, P. Be na do, F. Bazza elli, N. B. McKeown, Science 2013,339, 303–307; b) Y. Rogan, R. Malpass-E ans, M. Ca a, Angewand e Chemie Resea ch A icles Angew. Chem. In . Ed. 2023,62, e202215250 (8 o 9) © 2022 The Au ho s. Angewand e Chemie In e na ional Edi ion published by Wiley-VCH GmbH 15213773, 2023, 8, Downloaded om h ps://onlinelib a y.wiley.com/doi/10.1002/anie.202215250 by Readcube (Lab i a Inc.), Wiley Online Lib a y on [26/01/2024]. See he Te ms and Condi ions (h ps://onlinelib a y.wiley.com/ e ms-and-condi ions) on Wiley Online Lib a y o ules o use; OA a icles a e go e ned by he applicable C ea i e Commons License M. Lee, J. C. Jansen, P. Be na do, G. Cla izia, E. Tocci, K. F iess, M. Lanc, N. B. McKeown, J. Ma e . Chem. A 2014,2, 4874–4877; c) X. Ma, I. Pinnau, Mac omolecules 2018,51, 1069–1076. [10] a) B. S. Ghanem, R. Swaidan, E. Li wille , I. Pinnau, Ad . Ma e . 2014,26, 3688–3692; b) R. Swaidan, M. Al-Saeedi, B. Ghanem, E. Li wille , I. Pinnau, Mac omolecules 2014,47, 5104–5114; c) I. Rose, M. Ca a, R. Malpass-E ans, M. C. Fe a i, P. Be na do, G. Cla izia, J. C. Jansen, N. B. McKeown, ACS Mac o Le . 2015,4, 912–915; d) B. S. Ghanem, F. Alghunaimi, Y. G. Wang, G. Genduso, I. Pinnau, ACS Omega 2018,3, 11874–11882; e) G. Genduso, B. S. Ghanem, Y. Wang, I. Pinnau, Polyme 2019,11, 361; ) T. Zhang, L. Deng, P. Li, Ind. Eng. Chem. Res. 2020,59, 18640–18648; g) X. Ma, Z. Zhu, W. Shi, W. Ji, J. Li, Y. Wang, I. Pinnau, J. Ma e . Chem. A 2021,9, 5404–5414. [11] R. Williams, L. Bu , E. Esposi o, J. Jansen, E. Tocci, C. Rizzu o, M. Lanč, M. Ca a, N. McKeown, J. Ma e . Chem. A 2018,6, 5661–5667. [12] a) Z. Zhu, J. Zhu, J. Li, X. Ma, Mac omolecules 2020,53, 1573–1584; b) X. Ma, H. W. H. Lai, Y. Wang, A. Alhazmi, Y. Xia, I. Pinnau, ACS Mac o Le . 2020,9, 680–685; c) R. Malpass-E ans, I. Rose, A. Fuoco, P. Be na do, G. Cla izia, N. B. McKeown, J. C. Jansen, M. Ca a, Memb anes 2020,10, 62. [13] D. N. Bu le , A. Ba e e, R. A. Snow, Syn h. Commun. 1975, 5, 101–106. [14] a) M. Hong, L. Cui, S. R. Liu, Y. S. Li, Mac omolecules 2012, 45, 5397–5402; b) J. X. Yang, J. Cui, Y. Y. Long, Y. G. Li, Y. S. Li, J. Polym. Sci. Pa A 2014,52, 2654–2661. [15] S. V. Sho uno , M. A. Rudako a, M. E. Fil’kina, Y. V. Nelyu- bina, M. V. Be meshe , Pe . Chem. 2019,59, S88–S94. [16] a) T. M. Long, T. M. Swage , Ad . Ma e . 2001,13, 601–604; b) N. T. Tsui, A. J. Pa askos, L. To un, T. M. Swage , E. L. Thomas, Mac omolecules 2006,39, 3350–3358. [17] a) J. L. Pozzo, G. M. Cla ie , M. Colomes, H. Bouas-Lau en , Te ahed on 1997,53, 6377–6390; b) T. J. Co ado, Z. Huang, D. Huang, N. Wamble, T. Luo, R. Guo, P oc. Na l. Acad. Sci. USA 2021,118, e2022204118. [18] R. Sho , M. Ca a, C. G. Bezzu, D. F i sch, B. M. Ka iuki, N. B. McKeown, Chem. Commun. 2011,47, 6822–6824. [19] N. B. McKeown, Sci. China Chem. 2017,60, 1023–1032. [20] H. A. Pa el, C. T. Ya uz, Chem. Commun. 2012,48, 9989–9991. [21] C. Ye, R. Tan, A. Wang, J. Chen, B. Comesaña Gánda a, C. B eakwell, A. Al a ez-Fe nandez, Z. Fan, J. Weng, C. G. Bezzu, S. Guldin, N. P. B andon, A. R. Kuce nak, K. E. Jel s, N. B. McKeown, Q. Song, Angew. Chem. In . Ed. 2022,61, e202207580; Angew. Chem. 2022,134, e202207580. [22] a) K. Polak-K aśna, C. Fuh hop, S. Rocha , A. D. Bu ows, A. Geo giadis, C. R. Bowen, T. J. Mays, In . J. Hyd ogen Ene gy 2017,42, 23915–23919; b) M. Longo, M. P. De San o, E. Esposi o, A. Fuoco, M. Mon eleone, L. Gio no, B. Comesana- Ganda a, J. Chen, C. G. Bezzu, M. Ca a, I. Rose, N. B. McKeown, J. C. Jansen, Ind. Eng. Chem. Res. 2020,59, 5381– 5391. [23] R. Swaidan, B. S. Ghanem, E. Li wille , I. Pinnau, J. Memb . Sci. 2014,457, 95–102. [24] M. Longo, B. Comesaña-Gánda a, M. Mon eleone, E. Esposi- o, A. Fuoco, L. Gio no, N. B. McKeown, J. C. Jansen, J. Memb . Sci. Res. 2022,8, 540493. [25] A. Fuoco, B. Comesana-Ganda a, M. Longo, E. Esposi o, M. Mon eleone, I. Rose, C. G. Bezzu, M. Ca a, N. B. McKeown, J. C. Jansen, ACS Appl. Ma e . In e aces 2018,10, 36475– 36482. [26] V. Teplyako , P. Mea es, Gas Sep. Pu i . 1990,4, 66–74. [27] A. Fuoco, C. Rizzu o, E. Tocci, M. Mon eleone, E. Esposi o, P. M. Budd, M. Ca a, B. Comesaña-Gánda a, N. B. McKeown, J. C. Jansen, J. Ma e . Chem. A 2019,7, 20121–20126. [28] S. C. F aga, M. Mon eleone, M. Lanč, E. Esposi o, A. Fuoco, L. Gio no, K. Pilnáček, K. F iess, M. Ca a, N. B. McKeown, P. Izák, Z. Pe uso á, J. G. C espo, C. B azinha, J. C. Jansen, J. Memb . Sci. 2018,561, 39–58. [29] R. Swaidan, B. Ghanem, E. Li wille , I. Pinnau, Mac o- molecules 2015,48, 6553–6561. [30] A. Fuoco, B. Sa ilmis, T. Uya , M. Mon eleone, E. Esposi o, C. Muzzi, E. Tocci, M. Longo, M. P. D. San o, M. Lanč, K. F iess, O. Vopička, P. Izák, J. C. Jansen, J. Memb . Sci. 2020,594, 117460. [31] R. R. Tiwa i, J. Jin, B. D. F eeman, D. R. Paul, J. Memb . Sci. 2017,537, 362–371. [32] K. Miz ahi Rod iguez, F. M. Benede i, N. Roy, A. X. Wu, Z. P. Smi h, J. Ma e . Chem. 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