Intramolecular Quaternization as Folding Strategy for the Synthesis of Catalytically Active Imidazolium-based Single Chain Nanoparticles

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1 Supporting Informtion Intrmolulr Qutrniztion s Foling Strtgy for th Synthsis of Ctlytilly Ativ Imizolium-s Singl Chin Nnoprtils Romin Lmrt,, Ann-Lur Wirotius,, n Dnil Tton, * Lortoir Chimi s Polymèrs Orgniqus Univrsité Borux IPB-ENSCBP, F Pss Cx, Frn Lortoir Chimi s Polymèrs Orgniqus Cntr Ntionl l Rhrh Sintifiqu 16 Avnu Py-Brln, F Pss Cx, Frn KEYWORDS: Singl hin nnoprtils, foling, imizolium, N-htroyli rn, RAFT. Mtrils Bnzimizol ( 95%), 4-vinylnzyl hlori (90%), thyl romi (99%), lithium is(trifluoromthn)sulfonylimi n 4-yno-4-(phnylronothioylthio)pntnoi i (CPAD, 97%) wr otin from Alrih n us s riv. Th hyroxy-ontining poly(thyln oxi) monomthylstr (CH 3 O-PEO 16 -OH, 800 g.mol -1 ) ws otin from Alrih n us s riv. Azois(2-mthylpropionitril) (AIBN, 99%) ws riv from Alrih n ws purifi y rrystlliztion from mthnol. Styrn n imthylformmi wr ri ovr CH 2 n istill prior to us. 1,3-Diylohxylroiimi (DCC, 99%) ws otin from Alf Asr n 4- imthylminopyriin (DMAP; 99%) ws otin from TCI n us s riv. Ttrhyrofurn (THF) ws istill ovr N/nzophnon. Ethyl tt n tonitril (99.7%, Alrih) wr us without furthr purifition. Mthnol ws istill ovr mtlli N prior to us. Instrumntl nlyss 1 H NMR, 13 C NMR sptr wr ror on Brukr AC-400 sptromtr in pproprit utrt solvnts. All 13 C msurmnts wr prform t 298 K on Brukr Avn III 400 sptromtr oprting t MHz n quipp with 5 mm Brukr multinulr irt ryopro. All DOSY (Diffusion Orr SptrosopY) 1,2 msurmnts wr prform t 298K on Brukr Avn III HD 400 sptromtr oprting t MHz n quipp with 5mm Brukr multinulr z- grint irt ryopro-h pl of prouing grints in th z irtion with strngth 53.5 G m -1. For h smpl, 3 mg ws issolv in 0.4 µl of DMSO-6 for intrnl lok n spinning ws us to minimiz onvtion ffts. DOSY sptr wr quir with th lpgp2s puls progrm from Brukr topspin softwr. Th urtion of th puls grints n th iffusion tim wr

2 just in orr to otin full ttnution of th signls t 95 % of mximum grint strngth. Th vlus wr 2.0 ms for th urtion of th grint pulss n 300 ms for th iffusion tim. Th grints strngth ws linrly inrmnt in 16 stps from 5% to 95% of th mximum grint strngth. A ly of 3 s twn hos ws us. Th t wr pross using 8192 points in th F2 imnsion n 256 points in th F1 imnsion with th Brukr topspin softwr. Fil grint lirtion ws omplish t 25 C using th slf-iffusion offiint of H 2 O+D 2 O t 19.0 x m 2.s -1. 3,4 (1) Johnson C.S., Prog. Nul. Mgn. Rson. Sptros., 1999, 34, 203 (2) Stils P., Anl. Chm., 1981, 53, (3) Holz M., Wingärtnr M., J. Mgn. Rson., 1991, 92, (4) Longswoth L. G., J. Phys. Chm., 1960, 64, Synthsis of 4-vinylnzylnzimiol 2. Bnzimizol (6 g, 51 mmol) ws issolv in DMF (50 ml) n 5.72 g of potssium hyroxi wr (2 q., 102 mmol). Th solution ws stirr for 30 minuts n 7.75 ml (8.3 g, 55 mmol) of 4-vinylnzylhlori wr rop-wis. Aftr stirring t room tmprtur for 24h, th solution ws ilut with 50 ml of wtr n xtrt with hloroform (6 x 25 ml). Orgni phss wr omin, ri ovr MgSO 4 n vport, yiling yllow visous oil (11.9 g, 44 mmol, yil = 90 %) (Figur S1). Figur S1: 1 H NMR sptrum of 4-vinylnzylnzimiol 2 in DMSO-6 Synthsis of 4-vinylnzyl-H-nzimiolium 3. 4-vinylnzylnzimiol 1 (11.8 g, 44 mmol) ws issolv in 20 ml of mthnol n fw rops of HCl wr slowly. Aftr stirring 24h t room tmprtur, th solvnt ws rmov ling to whit powr (11.3 g, 42 mmol, yil = 95%) (Figur S2).

3 DMSO Figur S2: 1 H NMR sptrum of 4-vinylnzyl-H-nzimiolium 3 in DMSO-6 Synthsis of 4-vinylnzyl-PEO Th hyroxy-ontining poly(thyln oxi) monomthylstr (CH 3 O-PEO 16 -OH, 800 g.mol -1 ) (10 g, 12.5 mmol) ws issolv in THF (30 ml) n lrg xss of NH (10 q., 3 g, 125 mmol) ws slowly. Aftr 30 min stirring, 1.80 ml (1.95 g, 13 mmol) of 4- vinylnzylhlori wr rop-wis. Th rtion ws stirr t 50 C for 48h n thn pripitt thr tims in lrg xss of ithyl thr. Th pur prout ws isolt s yllow visous oil (8.1 g, 9.3 mmol, yil = 75%) (Figur S3). f f DMSO Wtr Figur S3: 1 H NMR sptrum of 4-vinylnzyl-PEO 16 4 in DMSO-6

4 Synthsis of PS-o-PImH(Cl)-o-PS/PEO-o-PVBnzCl 7. Th CTA (6, 23 mg, mmol), styrn (5, 300 mg, 2.9 mmol) 4-vinylnzyl-H-nzimizolium hlori (3, 310 mg, 1.15 mmol), 4- vinylnzylhlori (1, 176 mg, 1.15 mmol), 4-vinylnzyl-PEO 16 (4, 500 mg, 0.58 mmol), n AIBN (6.0 mg, mmol) wr issolv in mthnol. Th solution ws gss y fiv sussiv frz-pump yls n stirr for 24h t 80 C. Th s-otin opolymr ws purifi y ilysis ginst mthnol (1 kd mmrn) n otin s pink powr (m = 936 mg); onvrsion = 78 %, yil = 66 %, (Figur S4). + ) ) ) Figur S4: 1 H NMR sptr of 7 (), 8 () n 9 () in DMSO-6. Dprottion of PS-o-PImH(Cl)-o-PS/PEO-o-PVBnzCl 8. Polymr 7 ws issolv in mthnol n lrg xss of K 2 CO 3 ws. ftr 24h stirring t 40 C, th solution ws purifi y ilysis ginst mthnol (1 kd mmrn) n th trgt polymr 8 otin s pink powr (m = 890 mg); yil = 95 %, (Figur S4). Synthsis of SCNPs-Cl 9. Polymr 8 (50 mg) ws issolv in 100 ml of ry THF in Shlnk tu. Th solution ws stirr t 80 C for 48h n thn th solvnt ws vport ling to SCNPs-Cl 9 (712 mg, yil = 80%), (Figur S4). Synthsis of SCNPs-OA 10. SCNPs-Cl 9 (712 mg) ws issolv in 5 ml of ry mthnol n lrg xss of ry potssium tt ws. Aftr 24h stirring t 40 C th solution ws filtr unr lit in orr to rmov inorgni slts n thn ilys ginst mthnol (1 kd mmrn). Th solvnt ws rmov unr ru prssur. SCNPs-OA 10 ws otin s pink powr (570 mg, yil = 80%), (Figur S5-S5).

5 Figur S5: 1 H NMR sptrum of SCNPs-OA 10 in DMSO-6 Figur S5: 13 C NMR sptrum of SCNPs-OA 10 in DMSO-6

6 Bnzoin onnstion. In typil xprimnt, 10 ws introu in Shlnk tu. Th soli mixtur ws llow to stir for 1 h unr vuum, n th flsk ws sujt to thr frz-thw Ar/vuum yls. A 5 ml portion of solvnt (THF or wtr) n thn 0.5 ml (5 mmol) of nzlhy wr thn. Th rtion mixtur ws stirr for 24 h t 80 C. Th mixtur ws llow to ool own to room tmprtur, n ws filtr unr vuum. Th filtrt ws nlyz y 1 H NMR in CDCl 3. Bnzoin onvrsion ws trmin y 1 H NMR in CDCl 3 y ompring th intgrl vlu of th lhy signl of nzlhy (, 10 ppm) with tht of th -CH- nzoin signl (, 6 ppm). Th rovr polymr ws suspn in THF n rus for nxt run of tlysis, (Figur S6). 10 THF THF CHCl 3 ++ Figur S6: 1 H NMR sptrum of nzoin onnstion rtion in CDCl 3

7 DOSY msurmnt: D = R = kt 6. π. η. R. f(t) kt D. 6. π. η. f(t) f(t) = 1 R = kt D. 6. π. η k = 1.38x10 23 J.K -1 D = m 2 /s T = 298K η DMSO visosity η DMSO = P.s R = 3.8 nm D = 7.6 nm.