Supporting Informtion A Strightforwr Protool for the Highly Effiient Preprtion of Min-hin Azo Polymers Diretly from Bisnitroromti Compouns y the Phototlyti Proess Liing Wng, Xingqing Pn, Yin Zho, Yng Chen, Wei Zhng,* Yingfeng Tu, Zhengio Zhng, Jin Zhu, inhen Zhou, n Xiulin Zhu Suzhou Key Lortory of Mromoleulr Design n Preision Synthesis, Jingsu Key Lortory of Avne Funtionl Polymer Design n Applition, College of Chemistry, Chemil Engineering n Mterils Siene, Soohow University, Suzhou Inustril Prk, Suzhou 215123, Chin. Emil: weizhng@su.eu.n 1
Experimentl Setion Synthesis Sheme S1. Syntheti routes of 1,2-is(4-(hexyloxy)phenyl)izene (HOPA) n 1,2-is(9,9-iotyl-9H-fluoren-2-yl)izene (OFLA). Synthesis of 1-(hexyloxy)-4-nitroenzene (HOB) A mixture of 4-nitrophenol (4.1 g, 0.03 mol), potssium ronte (5.5 g, 0.04 mol), romohexne (3.3 g, 0.02 mol) n DMF (100 ml) were stirre for 10 h t 80 o C. After ooling own to room temperture, n-hexne (100 ml) ws e. The mixture ws wshe with eionize wter twie. After eing rie over nhyrous MgSO 4 overnight, the solution ws evporte uner reue pressure. The prout ws rerystllize from ool n-hexne n rie uner vuum to ffor white soli s prout HOB (3.6 g, yiel: 80%). 1 H MR (300 MHz, CD 3 Cl), δ (TMS, ppm): 8.25, 6.93 (4H, Ar-H), 4.09 (2H, OCH 2 ), 1.81 (2H, OCH 2 -CH 2 ), 1.25-1.61 (4H, CH 2 ), 0.88 (3H, CH 3 ). Synthesis of 1,2-is(4-(hexyloxy)phenyl)izene (HOPA) To mixture of HOB (100 mg) n potssium hyroxie (5.6 mg) in mixe solvents of 3 ml toluene n 3 ml isopropyl lohol ws e tlyst (33 mg) uner room temperture. The solution ws ule with rgon for 10 minutes, then the mpule ws flme sele n mgnetilly strrie uner the illumintion of Xe lmp t 45 o C for 8 h. The mpoule ws opene n the resulting mixture ws purifie y sili gel olumn hromtogrphy eluting with ethyl ette/petroleum ether (v/v, 1/50) to ffor right yellow soli s prout HOPA (81 mg, yiel: 95%). 1 H MR (300 MHz, CD 3 Cl), δ (TMS, ppm): 7.82, 7.01 (8H, Ar-H), 4.09 (4H, OCH 2 ), 1.82 (4H, OCH 2 -CH 2 ), 1.25-1.61 (8H, CH 2 ), 0.88 (6H, CH 3 ). 13 C MR (100 MHz, CD 3 Cl, δ): 161.34, 146.92, 124.38, 114.67, 68.43, 31.64, 29.18, 25.87, 22.78, 14.06. 2
Synthesis of 2-nitro-9H-fluorene (FL) 9H-fluorene (4.0 g) ws e to the solution of 10 ml HO 3 (65%) n 50 ml 1,2-ihloroethne t 0 o C. After 10 minutes, the prout ws otine y filtrtion n then rerystllize from ethnol, n rie uner vuum to get primrose yellow soli FL (4.6 g, yiel: 90%). 1 H MR (300 MHz, CD 3 Cl), δ (TMS, ppm): 8.40 8.30, 7.88, 7.86, 7.63, 7.47, 7.44 (7H, Ar-H), 4.01 (4H, CH 2 ). Synthesis of 2-nitro-9,9-iotyl-9H-fluorene (OFL) 2-itro-9,9-iotyl-9H-fluorene (OFL) ws prepre with the similr proeure to tht of HOB. The rue prout ws purifie y sili gel olumn hromtogrphy eluting with ethyl ette/petroleum ether (v/v, 1/100) to ffor right yellow oil s prout OFL (3.0 g, yiel: 70%). 1 H MR (300 MHz, CD 3 Cl), δ (TMS, ppm): 8.27, 8.24, 8.20, 7.78, 7.40 (7H, Ar-H), 2.02 (4H, CH 2 CCH 2 ), 0.93-1.33 (20H, CH 2 ), 0.81 (6H, CH 3 ), 0.57 (4H, CH 2 CH 3 ). Synthesis of 1,2-is(9,9-iotyl-9H-fluoren-2-yl)izene (OFLA) 1,2-Bis(9,9-iotyl-9H-fluoren-2-yl)izene (OFLA) ws prepre with the similr proeure to tht of HOPA. The prout ws purifie y sili gel olumn hromtogrphy eluting with ethyl ette/petroleum ether (v/v, 1/40) to ffor right yellow soli s prout OFLA (78 mg, yiel: 96%). 1 H MR (300 MHz, CD 3 Cl), δ (TMS, ppm): 7.96, 7.84, 7.75, 7.35 (14H, Ar-H), 2.06 (4H, CH 2 CCH 2 ), 0.90-1.32 (40H, CH 2 ), 0.79 (12H, CH 3 ), 0.65 (8H, CH 2 CH 3 ). 13 C MR (100 MHz, CD 3 Cl, δ): 152.49, 151.86, 144.02, 140.34, 127.85, 127.02, 122.85, 120.39, 120.11, 117.12, 55.43, 40.51, 31.82, 30.09, 29.26, 23.84, 22.63. H O OC 12 H 25 C 12 H 25 MgBr Et 2 O C 12 H 25 OH C 12 H 25 TsCI/Me 3 HCI/Et 3 OTs CH 2 CI C 12 H 25 C 12 H 25 2 O2 O 2 KOH Cu(O 3 ) 2 DMSO HA/A 2 O C 12 H 25 C 12 H 25 C 12 H 25 C 12 H 25 PECZ Monomer B Sheme S2. Syntheti routes of 3,6-initro-9-(pentosn-13-yl)-9H-rzole (monomer B). 3
Synthesis of 9-(pentosn-13-yl)-9H-rzole (PECZ) The syntheti metho of PECZ is similr to the metho esrie in the referene. S1 Yiel, 50%. 1 H MR (300 MHz, CD 3 Cl), δ (TMS, ppm): 8.10, 7.56, 7.40, 7.20 (8H, Ar-H). 4.54 (1H, CH), 2.27 (2H, CH 2 -CH), 1.90 (2H, CH 2 -CH), 1.40-0.90 (40H, CH 2 ), 0.86 (6H, CH 3 ). Synthesis of 3,6-initro-9-(pentosn-13-yl)-9H-rzole (monomer B) Cu(O 3 ) 2 2.5H 2 O (0.65 g, 2.9 mmol) ws e into the mixture of eti i (10 ml) n eti nhyrie (10 ml) t room temperture. After stirring for 15 min, PECZ (0.51 g, 1.0 mmol) ws e n the mixture ws ontinuously stirre for 12 h. After tht, the retion mixture ws poure into 200 ml wter n the yellowish preipitte ws filtere. Then the rue prout ws purifie y sili gel olumn hromtogrphy eluting with ethyl ette/petroleum ether (v/v, 1/10) to ffor yellowish soli s prout monomer B (0.42 g, yiel: 70%). 1 H MR (300 MHz, CD 3 Cl), δ (TMS, ppm): 9.10, 8.46, 7.70, 7.52 (6H, Ar-H). 4.65 (1H, CH), 2.26 (2H, CH 2 -CH), 2.03 (2H, CH 2 -CH), 1.30-0.90 (40H, CH 2 ), 0.85 (6H, CH 3 ). 13 C MR (100 MHz, CD 3 Cl, δ): 146.24, 143.04, 141.61, 123.54, 122.96, 122.40, 122.08, 117.45, 112.16, 109.78, 58.25, 33.69, 31.76, 29.57, 29.49, 29.40, 29.30, 29.28, 29.21, 26.74, 22.62. Elementl Anlysis: Cl. (%) for C 37 H 57 3 O 4 : C, 73.11; H, 9.45;, 6.91. Foun (%): C, 72.74; H, 9.51;, 6.76. Sheme S3. Syntheti routes of 1,12-is(2-(oeyloxy)-4-nitrophenoxy)oene (monomer C). Synthesis of 2-(oeyloxy)phenol (DPH) A mixture of potssium ronte (15 g, 0.11 mol) n DMF (200 ml) were stirre for 30 minutes. Then 2-hyroxyphenol (12 g, 0.11 mol) n 1-romooene (20 g, 0.08 mol) were e n the retion ws onute t 80 o C for 10 h. The resulting mixture ws oole own to room temperture n poure into ie wter. Filtere to otin the rue prout n purifie y sili gel olumn hromtogrphy 4
eluting with ethyl ette/petroleum ether (v/v, 1/20) to ffor white soli s prout DPH (14 g, yiel: 64%). 1 H MR (300 MHz, CD 3 Cl), δ (TMS, ppm): 6.91, 6.88, 6.83 (4H, Ar-H). 3.98 (2H, OCH 2 ), 3.73 (1H, OH), 1.81 (2H, OCH 2 -CH 2 ), 1.51-1.12 (18H, CH 2 ), 0.88 (3H, CH 3 ). Synthesis of 1,12-is(2-(oeyloxy)phenoxy)oene (DPHD) DPHD ws synthesize using similr proeure s esrie for the synthesis of DPH. A white soli ws otine (2.4 g, yiel: 32%). 1 H MR (300 MHz, CD 3 Cl), δ (TMS, ppm): 7.00-6.81 (8H, Ar-H). 4.01 (8H, OCH 2 ), 1.82 (8H, OCH 2 -CH 2 ), 1.55-1.15 (52H, CH 2 ), 0.89 (6H, CH 3 ). Synthesis of 1,12-is(2-(oeyloxy)-4-nitrophenoxy)oene (monomer A) Cu(O 3 ) 2 2.5H 2 O (1.38 g, 6.2 mmol), eti i 10 ml n eti nhyrie10 ml were ple in 50 ml roun ottom flsk t room temperture. After stirring for 15 min, DPHD (1.44 g, 2.0 mmol) ws e to the mixture n the solution ws kept t 50 o C for 12 h. After ooling to room temperture, the retion mixture ws poure into ie n the yellowish preipitte ws filtere. Then the resiue ws purifie y sili gel olumn hromtogrphy eluting with ethyl ette/petroleum ether (1/5) to ffor yellowish soli s prout monomer C (0.96 g, yiel: 60%). 1 H MR (300 MHz, CD 3 Cl), δ (TMS, ppm): 7.88, 7.72, 7.26, 6.86 (6H, Ar-H). 4.08 (8H, OCH 2 ), 1.87 (8H, OCH 2 -CH 2 ), 1.48-1.14 (52H, CH 2 ), 0.86 (6H, CH 3 ). 13 C MR (100 MHz, CD 3 Cl, δ): 154.8, 148.7, 141.0, 117.6, 111.0, 108.2, 69.3, 31.93, 29.70, 29.67, 29.61, 29.38, 29.36, 29.33, 28.97, 28.95, 28.93, 25.96, 25.92, 22.69. Elementl Anlysis: Cl. (%) for C 48 H 80 2 O 8 : C, 70.90; H, 9.92;, 3.45. Foun (%): C, 70.45; H, 9.78;, 3.16. 5
Figure S1. The trnsmission eletron mirosopy (TEM) imge of ZrO 2 -supporte AuPs (3 wt%). () O 2 O e () O O e e e 9 8 7 6 5 4 3 2 1 0 Chemil shift (ppm) 9 8 7 6 5 4 3 2 1 0 Chemil shift (ppm) Figure S2. 1 H MR spetr of HOB () n HOPA () in CDCl 3. () O 2 C 6H 13 e C 6H 13 e () C 8H 17 C 6H 13 e C 6H 13 C 8H 17 e 9 8 7 6 5 4 3 2 1 0 Chemil shift (ppm) 9 8 7 6 5 4 3 2 1 0 Chemil shift (ppm) Figure S3. 1 H MR spetr of OFL () n OFLA () in CDCl 3. 6
Figure S4. 13 C MR spetr of HOPA () n OFLA () in CDCl 3. Tle S1. Phototlyze reution of nitroromti ompouns in ifferent experimentl onitions. Entry Seon solvent Seon solvent (ml) Conv. (%) Yiel 1 none 0 100 >98 2 DCM 3 98 18 3 hloroform 3 0 0 4 etone 3 99 32 5 THF 3 97 27 6 nisole 3 99 81 7 MCB 3 100 >97 8 toluene 3 100 >99 9 toluene 4 99 70 Retion onitions: isopropyl lohol (3 ml), HOB (80 mg), tlyst (33 mg), KOH (5.6 mg), 8 h. The phototlyze retions were onute in n rgon tmosphere t 45 o C. Yiels mesure y HPLC nlysis. Isopropyl lohol (6 ml). 7
HOB hv AuPs HOPA hv Yiel 95% OFL AuPs OFLA Figure S5. The solution olor hnges efore n fter the phototlyze retion. () O2 e O2 () O 2 OC 12H25 e O C 12H 25O O O 2 C1 H2 C1 H2 e e e 10 9 8 7 6 5 4 3 2 1 0 Chemil shift (ppm) 8 7 6 5 4 3 2 1 0 Chemil shift (ppm) Figure S6. 1 H MR spetr of the monomer B () n monomer C () in CDCl 3. Figure S7. 13 C MR spetr of the monomer B () n monomer C () in CDCl 3. 8
M n,gpc (PC) = 4600 g/mol, PDI = 1.50 M n,gpc (PA) = 28000 g/mol, PDI = 2.63 M n,gpc (PB) = 4100 g/mol, PDI = 1.16 8 9 10 11 12 13 14 15 16 17 Retentin time (min) Figure S8. The GPC tres of Azo polymers (PA, PB n PC). Tle S2. Phototlyze polyonenstion of isnitroromti monomers C uner ifferent experimentl onitions. Entry Ctlyst/KOH (m/m, mg) t (h) Conv. (%) M n,gpc (g/mol) PDI 1 33/5.6 2 34 2500 2.34 2 33/5.6 4 38 2900 1.13 3 33/5.6 8 82 3000 1.22 4 33/5.6 12 90 4800 1.71 5 33/5.6 24 92 4600.1.50 6 66/11.2 24 89 3200 1.34 7 33/5.6 24 85 3300 1.39 8 33/5.6 4 58 4500 1.15 9 33/5.6 8 92 4600 1.23 10 33/5.6 12 96 4800 1.26 11 33/5.6 24 95 4100 1.16 The phototlyze polyonenstion retions were rrie out with 80 mg isnitroromti monomers C in n rgon tmosphere t 45 o C. Isopropyl lohol (3 ml), toluene (3 ml), tlyst (33 mg), KOH (5.6 mg). Bisnitroromti monomers (60 mg). Bisnitroromti monomers B. 9
Figure S9. The FT-IR spetr of isnitroromti monomers (A, B n C) n orresponing polymers (PAs, PBs n PCs) with ifferent retion time. () () 10 9 8 7 6 5 4 3 2 1 0 Chemil shift (ppm) 10 9 8 7 6 5 4 3 2 1 0 Chemil shift (ppm) Figure S10. 1 H MR spetr of PB-24h (M n,gpc = 4100 g/mol, PDI = 1.16) () n PC-24h (M n,gpc = 4600 g/mol, PDI = 1.50) () in CDCl 3. 10
PB-4h M = [M + ] + : Cl: 3404.6 Foun: 3404.1 [M + ] + -[] 3427.1 559.5 559.5 559.5 559.8 3986.6 3000 4000 5000 6000 7000 8000 m/z 3400 3600 3800 4000 m/z C 12 H 25 C 12 H 25 PB-24h M = O 2 5 O 2 C 12 H 25 C 12 H 25 [M + H] + : Cl: 3325.7 Foun: 3325.4 -[O] -[O] -[O] -[O] [M + H] + 3325.7 [M + O] + [M + ] + [M + K] + 543.5 543.5 2000 3000 4000 5000 6000 7000 m/z photoegrtion prout 3869.2 3300 3400 3500 3600 3700 3800 3900 m/z 11
Figure S11. MALDI-TOF-MS spetr of PBs n PCs t ifferent retion time. () 1.2 (404 nm) 0 s () 1.0 As 1.0 0.8 0.6 0.4 70 s As 0.8 0.6 0.4 180 s 0 s (546 nm) 0.2 0.2 0.0 300 350 400 450 500 550 600 Wvelength (nm) 0.0 250 300 350 400 450 500 550 600 Wvelength (nm) Figure S12. Asorption spetr of PB-24h solution uring ontinuous 404 nm () n 546 nm () light irrition in THF. The onentrtion of PB-24h (M n,gpc = 4100 g/mol, PDI = 1.16) is 0.05 g/l. 12
As () 1.0 (365 nm) 0.8 0.6 0.4 0.2 0 s 35 s As () 0.6 0.5 0.4 0.3 0.2 0.1 180 s 0 s (435 nm) 0.0 250 300 350 400 450 500 550 600 Wvelength (nm) 0.0 250 300 350 400 450 500 550 600 Wvelength (nm) Figure S13. Asorption spetr of PC-24h solution uring ontinuous 365 nm () n 435 nm () light irrition in THF. The onentrtion of PC-24h (M n,gpc = 4600 g/mol, PDI = 1.50) is 0.02 g/l. 1.4 1.2 As 1.0 0.8 0.6 0.4 0.2 Fresh 1 st -reyle 2 n -reyle 0.0 200 300 400 500 600 700 800 Wvelength (nm) Figure S14. UV-vis iffuse refletne spetrum of the reyle phototlysts. Figure S15. The trnsmission eletron mirosopy (TEM) imges of the reyle phototlysts. 13
REFERECE S1. Blouin,.; Mihu, A.; Leler, M. Av. Mter. 2007, 19, 2295-2300. 14