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1 Supporting Informtion Prision Synthsis of Imin-Funtionliz Rvrsil Mirogl Str Polymrs vi Dynmi Covlnt Cross-Linking of yrogn-boning Blok Copolymr Mills Yusuk Azum, Tky Trshim*, n Mitsuo Swmoto* Dprtmnt of Polymr Chmistry, Grut Shool of Enginring, Kyoto Univrsity Ktsur, ishikyo-ku, Kyoto , Jpn Tl/Fx: E-mil: trshim@living.polym.kyoto-u..jp; swmoto@str.polym.kyoto-u..jp *: orrsponing uthors Contnts Exprimntl Stion S2 Supporting Dt Figur S. Figur S2. MR sptr of ApUMA n ifuntionl linkr S6 MR sptr of trifuntionl linkr in DMS- 6 S7 Figur S3. Synthsis of MMA 25 /ApUMA 8 lok opolymr (P) S8 Figur S4. IR sptr of imin-mirogl str n lok (o)polymrs S9 Figur S5. MR sptr of n imin-mirogl str polymr S9 Figur S6. SEC n DLS of imin-mirogl str polymrs otin with P S0 Figur S7. Synthsis of imin-mirogl str polymrs vi rm-linking mtho S0 Figur S8. Synthsis of imin-mirogl str polymrs with P4, P5, n P6 S Figur S9. SEC of imin-mirogl str polymrs with P5 S Tl S. Synthsis of imin-mirogl str polymrs in vrious mix solvnts S2 Figur S0. UV-vis sptr of n imin-mirogl str polymr in th prsn of TFA S3 Figur S. UV-vis sptr of imin-mirogl str n lok (o)polymrs S3 Figur S2. SEC n MR sptr of prouts otin vi trnsmintion of S3 S4 Figur S3. Post-funtionliztion of S3 with -pyrnroxlhy S4 S

2 Exprimntl Stion Mtrils Mthyl mthrylt (MMA, TCI, purity > 99.8%) n thyl-2-hloro-2-phnyltt (Alrih, purity >98%) wr purifi y istilltion (MMA: from lium hyri) unr ru prssur for us. Chlorin-pp poly(mthyl mthrylt)s (PMMA-Cl) wr prpr vi Ru(In)Cl(PPh 3 ) 2 /n-bu 3 -tlyz living ril polymriztion of MMA oring to th litrtur. S 4-Dimthylmino--utnol (4-DMAB: TCI, purity >98%) ws purg y rgon for us. RuCp*Cl(PPh 3 ) 2 (Alrih) ws us s riv n hnl in glov ox unr moistur- n oxygn-fr rgon tmosphr ( 2 < ppm, 2 < ppm). Tolun ws purifi y pssing it through purifition olumn (Glss Contour Solvnt Systms y SG Wtr, USA).,-Dimthylformmi (DMF, Wko, hyrt, purity > 99.5%) n ihloromthn (Wko, hyrt) wr purg y rgon for us. A rgnrt llulos ilysis mmrn (Sptr/Por 7: molulr wight ut off 000) ws us s riv.,4-diminonzn (TCI, purity > 98.0%), 2-isoyntothyl mthrylt (IEMA: SWA DEK, purity >97%), trphthllhy (, TCI, purity > 98.0%), nzn-,3,5-triroxlhy (2, Alrih, purity >97%), soium ront (Wko, purity >99.5%), tonitril (Wko, hyrt, purity >99.8%), ttrhyrofurn (TF, Wko, hyrt, purity >99.5%), ton (Wko, hyrt, purity >99.5%), trifluoroti i (TFA, Wko, purity >98%), 2,4-imthoxynzlhy (TCI, purity >98 %), n-utylmin (TCI, purity >98%), n -pyrnroxlhy (TCI, purity >98%) wr us s riv. ApUMA [2-(3-(4-minophnyl)urio)thyl mthrylt], ur/imin ifuntionl linkr (3), n ur/imin trifuntionl linkr (4) wr synthsiz s shown low. Chrtriztion Th MWD, M n, n M w /M n rtios of polymrs wr msur y SEC in DMF ontining 0 mm LiBr t 40 o C (flow rt: ml/min) on thr linr-typ polystyrn gl olumns (Shox KF-805L: xlusion limit = ; prtil siz = 0 µm; por siz = 5000 Å; 0.8 m i.. 30 m) tht wr onnt to Jso PU-2080 prision pump, Jso RI-203 rfrtiv inx ttor, n Jso UV-2075 UV/vis ttor st t 270 nm. Th olumns wr lirt ginst 0 stnr poly(mma) smpls (Polymr Lortoris: M p = ; M w /M n =.02.09). nulr mgnti rsonn (MR) sptr ws ror in CDCl 3, DMS- 6, DMF- 7 t 25 o C on JEL JM-ECA500 sptromtr, oprting t ( ) Mz. Th solut wight-vrg molulr wight (M w ) of str polymrs ws trmin y multi-ngl lsr light sttring (MALLS) quipp with SEC in DMF ontining 0 mm LiBr t 40 o C on Dwn ELES II instrumnt (Wytt Thnology, smionutor lsr, λ = 663 nm). Th rfrtiv S2

3 inx inrmnt (n/) ws msur in DMF t 40 o C on n ptil DSP rfrtomtr (Wytt Thnology, l = 690 nm, < 2.5 mg/ml). Dynmi light sttring (DLS) msurmnts wr onut on tsuk Photl ELSZ-0 quipp with smionutor lsr (λ = 658 nm) t 25 o C ([polymr] = 0 mg/ml in DMF or C 2 Cl 2 ). Th msuring ngl ws 65 o n th t wr nlyz y CTI fitting mtho. Ultrviolt visil (UV/vis) sptr wr msur on Shimzu UV-800 in DMF t 25 o C (optil pth lngth =.0 m). Atomi for mirosopy (AFM) msurmnts wr onut y non-ontt tpping mo with Asylum Rsrh mol Cyphr ES. Silion ntilvrs (MCL-AC200TSA-C3E, lympus) with spring onstnts of 9 /nm (nominl rsonnt frquny of 50 kz) wr us n lirt y thrml flutution mtho. Pizoousti xittion is us to riv th ntilvr osilltion. Synthsis of ApUMA In 200 ml roun-ottom flsk quipp with thr-wy stopok,,4-iminonzn (53 mmol, 6.5 g) ws soluiliz in TF (270 ml) t 40 o C unr rgon. To this solution, TF solution (80 ml) of IEMA (5.0 mmol, 7.2 ml) ws ropwis t 40 o C. Aftr stirring t 40 o C for 2 h, th mixtur ws vport. Th rsulting ru ws rrystlliz in tonitril (20 ml) thr tims to giv whit soli ApUMA. Yil: 8.73 g (65%). MR [500 Mz, DMS- 6, r.t., δ = 2.5 ppm (CD 2 SCD 3 )]: δ 8.0 (, s, -CPh-), 7.0, 6.5 (4, m, romti), (, s, -CPh-), 6., 5.7 (2, s, olfin), 4.7 (2, s, -Ph 2 ), 4. (2, t, J = 5.7 z, -C 2 C 2 C-), (2, J = 5.4 z, -C 2 C 2 C-),.9 (3, s, -CC 3 ): ESI-MS m/z ([M + ] + ): l. for C , foun Synthsis of Ur/Imin Bifuntionl Linkr (3) In 00 ml roun-ottom flsk quipp with thr-wy stopok, trphthllhy (,.39 mmol, 86 mg) n ApUMA (2.92 mmol, 768 mg) ws mix in DMF (5 ml) t 25 o C unr rgon for 2 h. Aftr ition of DMF (3 ml) into th solution, th mixtur ws furthr stirr t 40 o C for 5 h. Th solution ws thn vport n th rsulting ru ws wsh with tonitril (00 ml) n ton (00 ml) to giv 3. Yil: 722 mg (83%). MR [500 Mz, DMS- 6, r.t., δ = 2.5 ppm (CD 2 SCD 3 )]: δ 8.7 (2, s, -CPhC-), 8.6 (2, s, -CPh-), 8.0 (4, m, romti), (4,, J = 8.6 z, romti), (4,, J = 8.6 z, romti), 6.3 (2, t, J = 5.7 z, -CPh-), 6., 5.7 (4, s, olfin), 4. (4, t, J = 5.7 z, -C 2 C 2 C-), (4, q, J = 5.3 z, -C 2 C 2 C-),.9.8 (4, s, -CC 3 ). Synthsis of Ur/Imin Trifuntionl Linkr (4) In 00 ml roun-ottom flsk quipp with thr-wy stopok, S3

4 nzn-,3,5-triroxlhy (2, 0.67 mmol, 00 mg) n ApUMA (3.70 mmol, 975 mg) wr stirr in DMF (5 ml) unr rgon t 40 o C for 48 h. Th mixtur ws thn vport n th rsulting ru ws wsh y tonitril (00 ml) n ton (00 ml) to giv 4. Yil: 407 mg (73%). MR [500 Mz, DMS- 6, r.t., δ = 2.5 ppm (CD 2 SCD 3 )]: δ 8.8 (3, s, -PhCPh-), 8.7 (3, s, -CPh-), 8.5 (3, s, romti), 7.4 (6,, romti, J = 8.9 z), 7.3 (6,, romti, J = 8.9 z,), 6.3 (3, t, J = 5.9 z), 6., 5.7 (6, olfin), 4. (4, t, J = 5.4 z, -C 2 C 2 C-), 3.4 (6, q, J = 5.6 z, -C 2 C 2 C-),.9 (9, s, -CC 3 ). Synthsis of MMA/ApUMA Blok Copolymrs MMA/ApUMA lok opolymrs (P-P6) wr synthsiz y syring thniqu unr rgon in k roun-ottom tu quipp with thr-wy stopok vi ruthnium-tlyz living ril polymriztion. A typil prour for MMA 25 /ApUMA 8 lok opolymr (P) ws givn: Chlorin-pp poly(mthyl mthrylt) (PMMA-Cl: M n = 2800, M w /M n =.3) ws first synthsiz vi ruthnium-tlyz living ril polymriztion oring to th prvious rport. S Thn, RuCp*Cl(PPh 3 ) 2 (0.05 mmol,.9 mg), ApUMA (.50 mmol, mg), n PMMA-Cl (0.50 mmol,.875 g) wr pl in 30 ml glss tu. Into this tu, DMF (.7 ml) n 500 mm DMF solution of 4-DMAB (0.60 mmol,.2 ml) wr squntilly t 25 o C unr rgon; th mixtur ws vigorously stirr. Th tu with th mixtur ws pl in n oil th kpt t 40 o C. Aftr 0 h, th rtion ws trmint y ooling th mixtur to -78 o C. Th onvrsion of ApUMA ws trmin s 78% y MR. Th ru prout ws purifi y ilysis in DMF for 3 ys to giv P. SEC: M n = 800 g/mol; M w /M n =.23. MR [500 Mz, DMF- 7, 25 o C. δ = 8.0 ppm (DMF)]: δ (-CPh-), (romti), (-CPh-), (-Ph 2 ), (-C 2 C 2 C-), (-CC 3 ), (-C 2 C 2 C-), 2..4 (-C 2 -) (3, s, -CC 3 ). M n (MR) = Synthsis of Imin-Mirogl Str Polymrs Imin-mirogl str polymrs wr synthsiz y syring thniqu unr rgon in roun-ottom flsk quipp with thr-wy stopok. A typil prour for S3 ws givn: In 50 ml roun-ottom flsk, P (0.02 mmol, 300 mg) n C 2 Cl 2 (5.5 ml) wr mix t 25 o C unr rgon for h. Into this tu, 5 mm C 2 Cl 2 solution of (0.075 mmol, 0.5 ml) ws t 25 o C unr rgon; th mixtur ws stirr. Aftr 24 h, th onvrsion of ws trmin s 95% y MR. SEC: str yil = 87%; M w = 5000 g/mol; M w /M n =.09. n/ (DMF) = SEC-MALLS (DMF, 0.0 M LiBr): M w,str = g/mol; rm (rm numr) = 20. DLS (DMF): R h = 9.2 nm. MR [500 Mz, DMF- 7, 25 o C. δ = 8.0 ppm S4

5 (DMF)]: δ (-PhCPh-, -CPh-), (romti), (-CPh-), (-C 2 C 2 C-), (-CC 3 ), (-C 2 C 2 C-), 2..4 (-C 2 -) (3, s, -CC 3 ). p-rsponsiv Domposition n R-Builing of Str Polymrs To ompos str polymr (S3), TFA (0.07 ml) n DMF/ 2 (/, v/v) mixtur (0.04 ml) wr squntilly into C 2 Cl 2 solution of S3 (40 mg, 2.0 ml) in 50 ml roun-ottom flsk t 25 o C. Th solution immitly turn to olorlss. Aftr stirring for h, th polymr solution ws irtly nlyz y GPC to onfirm th omposition into th orrsponing lok opolymr. To r-uil S3 from th ompos lok opolymr, 2 C 3 (0.754 mmol, 80.0mg) ws into th TFA/ 2 -trt trnsprnt solution (inluing ompos S3). Th mixtur ws thn stirr for 24h. Aftr filtrtion to rmov insolul 2 C 3, th mixtur ws irtly nlyz y SEC n SEC-MALLS to onfirm ruilt S3. SEC: str yil = 83%; M w = g/mol; M w /M n =.07. n/ (DMF) = SEC-MALLS (DMF, 0.0 M LiBr): M w,str = g/mol; rm = 25. Trnsimintion for Domposition of Str Polymrs Extr mounts of lhy or min wr mploy to inu trnsimintion of S3 in DMF. A typil prour ws givn: 2,4-imthoxynzlhy (62.3 mg, mmol) ws into DMF solution of S3 (5 mg,.5 ml) in 30 ml glss tu. Th mixtur ws stirr t 00 o C for 48 h. Thn, th formtion of orrsponing imin-funtionliz lok opolymr ws onfirm y SEC n MR (Figur S2). Anothr prour ws givn: n-utylmin (0.038 ml, mmol) ws into DMF solution of S3 (5 mg,.5 ml) in 30 ml glss tu. Th mixtur ws stirr t 25 o C for 24 h. Thn, th formtion of n originl MMA/ApUMA lok opolymr (P) ws onfirm y SEC n MR (Figur S2). Post-Funtionliztion of Str Polymrs with Alhys A 30 mm C 2 Cl 2 solution of -pyrnrlhy (0.7 mg, 0. ml) ws into DMF solution of S3 (20 mg, ml) in 30 ml glss tu. Th mixtur ws stirr t 00 o C for 2 h. Th prout ws pripitt into hxn to giv pyrn-ll S3. Th or-oun pyrn ws stimt s 5 mol% pr in-or ApUMA, onfirm y UV/vis (Figur S3). Rfrns S) Ko, Y.; Trshim, T.; omur, A.; uhi, M.; Swmoto, M. Mromoluls 20, 44, S5

6 Supporting Dt 2 2 C TF ApUMA 2 2 C DMF C 3 () ' ApUMA ' f g 2 h f g h () k ' l i j ' i j k l ppm Figur S. MR sptr of () ApUMA n () 3 in DMS- 6 t 25 o C. S6

7 C ' ApUMA 2 C 2 DMF C h i f g h ' i f g ppm Figur S2. MR sptrum of 4 in DMS- 6 t 25 o C. S7

8 () () Convrsion,% J J J J J Conv. Tim 78% (0 h) PMMA-Cl M n M w /M n 2700 (.3) 800 (.23) () Figur S3. 0 Cl 25 m M n (MR,) = 4800 M n (Conv) = 4900 f g m = Tim,h f g ppm Synthsis of MMA 25 /ApUMA 8 lok opolymr (P) vi ruthnium-tlyz living ril polymriztion of ApUMA with PMMA-Cl [() tim-onvrsion urv, () SEC urvs of PMMA-Cl n P, n () MR sptrum of P in DMF- 7 t 25 o C]: [ApUMA]/[PMMA-Cl]/ [RuCp*Cl(PPh 3 ) 2 ]/[4-DMAB] = 00/0/.0/40 mm in DMF t 40 o C MW (PMMA) 0 3 S8

9 () 00 Trnsmittn 93 Cl 25 8 MMA/ApUMA Blok Copolymr 2 Ur - (fr) - (-on) 00 Ur Wvnumr (m - ) Wvnumr (m - ) () - (fr) Imin-Cor Str Polymrs 3340(m - ) Ur - (-on) 300 Figur S4. IR sptr of () P n () S3 in C 2 Cl 2 t 25 o C: [Polymr] = 20 mg/ml. () Cl 25 8 ' 2 ' () Cl 25 8 ' f g ',,,g f, ppm Figur S5. MR sptr of () P n () S3 in DMF- 7 t 25 o C. S9

10 () S 96 h 24 h Solvnt [polymr] () S2 24 h C 2 Cl 2 mg/ml 24 h C 2 Cl 2 0 mg/ml () S6 96 h 24 h () S5 24 h DMF 50 mg/ml C 2 Cl 2 00 mg/ml 0 6 () MW (PMMA) MW (PMMA) R h Mill.0 nm.2 nm S D h (nm) D h (nm) Figur S6. SEC urvs of () S, () S2, () S6, () S5 (lk lins), thir intrmits (gry lins) n P (sh lin). DLS intnsity siz istriution of () P mill n (f) S2 in C 2 Cl 2 t 25 o C: [polymr] = 0 mg/ml. PMMA-Cl Cl 25 M n M w /M n Conv. 73% 5 h 3 UV (270 nm) Str Yil 6% Str MW (PMMA) PMMA-Cl RI 0 3 Figur S7. Synthsis of n imin-mirogl str polymr vi th linking rtion of PMMA-Cl with 3: [3]/[PMMA-Cl]/[Ru(In)Cl(PPh 3 ) 2 ]/[n-bu 3 ] = 50/0//20 mm in DMF t 80 o C. SEC urvs: soli lin y RI ttor n sh lin y UV ttor (270 nm). S0

11 253 () m 5 Mill R h 5.0 nm () M w,str rm Str Blok M w /M n Yil.9 87% (g) R h 4.8 nm () () (h) nm % 8.8 nm () (f) (i) nm % 29.9 nm D h (nm) D MW (PMMA) h (nm) Figur S8. (-, g-i) DLS intnsity siz istriution of lok (: P4, : P5, : P6) or str (g: S3, h: S6, i: S7) polymrs: [polymr] = 0 mg/ml in C 2 Cl 2 /DMF (90/0, v/v) t 25 o C. (-f) Synthsis of str polymrs (: S3, : S6, f: S7) vi th rosslinking of MMA/ApUMA lok opolymr mills (: P4, : P5, f: P6) with in C 2 Cl 2 /DMF (90/0, v/v) t 25 o C for 24 h. () Blok C 2 Cl S MW(PMMA) () C 2 Cl 2 /DMF (95/5) Blok S MW(PMMA) Figur S9. Synthsis of str polymrs (: S4, : S5) vi th rosslinking of MMA 253 /ApUMA 28 lok opolymr (P5) mill with in () C 2 Cl 2 or () C 2 Cl 2 /DMF (95/5, v/v) t 25 o C for 24 h. S

12 Tl S. Synthsis of Imin-Mirogl Str Polymrs in Vrious Mix Solvnts Co C 2 Cl 2 /DMF (v/v) Tim (h) Yil M w,str (MALLS) M w /M n (SEC) S8 00/ S9 98/ S20 95/ S2 90/ S22 80/ S23 50/ S24 20/ S25 0/ S26 2/ rm S27 0/ S8-S27: synthsiz y th rosslinking of lok opolymr (P2) mills with trphthllhy () in C 2 Cl 2 /DMF (00/0 0/00) mix solvnts t 25 o C: [- 2 ] 0 = [-C] 0 = /; [polymr] = 0 mg/ml. Str polymr yil stimt from th SEC urv r rtio of str polymrs to prouts. Asolut wight-vrg molulr wight (M w ) of str polymrs trmin y SEC-MALLS in DMF (0 mm LiBr). Molulr wight istriution of str polymrs trmin y SEC in DMF (0 mm LiBr) with PMMA stnr lirtion. Arm numrs ( rm ): [(wight frtion of rm) x M w,str (MALLS)]/M w,rm (SEC). S2

13 TFA C 2 Cl Asorn 0.5 TFA (mmol/ml) x x x x x Wvlngth (nm) Figur S0. UV-vis sptr of S3 in C 2 Cl 2 in th prsn of TFA t 25 o C: [S3] =.5 mg/ml (in-or imin = 7.5 x 0-4 mmol/ml); [TFA] = 0, 2, 5, 0, 20, 200 x 0-4 mmol/ml. Asorn 0.5 S3 ruilt S3 ompos S Wvlngth (nm) Figur S. UV-visil sptr of S3, ompos S3 (with TFA n 2 ), n ruilt S3 (y ing 2 C 3 ): [S3] =.0 mg/ml, [ompos S3] =.0 mg/ml, n [ruilt S3] = 0.85 mg/ml in DMF t 25 o C. S3

14 () S3 M M C () i' 25 i i C Cl 8 ' j C ' ' g M h f j g,g' M f' M i' M C h' g' f,f' h,h', ' ' ' () S3 2 MMA/ApUMA Blok Copolymr () 25 Cl 8 2 k l k l MW(PMMA) ppm Figur S2. (, ) SEC n (, ) MR sptr (in DMF- 7 t 25 o C) of prouts otin vi th trnsimintion of S3 with 2,4-imthoxynzlhy or n-utylmin. Asorn 0.5 S3 C Pyrn-Ll S3 -pyrnroxlhy Wvlngth (nm) Figur S3. UV-vis sptr of prout otin from post-funtionliztion of S3 with -pyrnroxlhy (30 mol% to S3-ring ApUMA units): [S3, pyrn-ll S3] =.0 mg/ml n [-pyrnroxlhy] = 0.0 mm in C 2 Cl 2 t 25 o C. S4