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-33607 Pss Cx, Frn Lortoir Chimi s Polymèrs Orgniqus Cntr Ntionl l Rhrh Sintifiqu 16 Avnu Py-Brln, F-33607 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 100.7 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 400.33 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
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 10-10 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, 2135-2137 (3) Holz M., Wingärtnr M., J. Mgn. Rson., 1991, 92, 115-125 (4) Longswoth L. G., J. Phys. Chm., 1960, 64, 1914-1917 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).
DMSO Figur S2: 1 H NMR sptrum of 4-vinylnzyl-H-nzimiolium 3 in DMSO-6 Synthsis of 4-vinylnzyl-PEO 16 4. 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
Synthsis of PS-o-PImH(Cl)-o-PS/PEO-o-PVBnzCl 7. Th CTA (6, 23 mg, 8.3.10-2 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, 4.0.10-2 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).
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
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
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 = 1.28.10-10 m 2 /s T = 298K η DMSO visosity η DMSO = 1.99. 10-3 P.s R = 3.8 nm D = 7.6 nm.