A Straightforward Protocol for the Highly Efficient Preparation of. Main-chain Azo Polymers Directly from Bisnitroaromatic Compounds

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1 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 , Chin. Emil: weizhng@su.eu.n 1

2 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 ), (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 ), (8H, CH 2 ), 0.88 (6H, CH 3 ). 13 C MR (100 MHz, CD 3 Cl, δ): , , , , 68.43, 31.64, 29.18, 25.87, 22.78,

3 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): , 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 ), (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 ), (40H, CH 2 ), 0.79 (12H, CH 3 ), 0.65 (8H, CH 2 CH 3 ). 13 C MR (100 MHz, CD 3 Cl, δ): , , , , , , , , , , 55.43, 40.51, 31.82, 30.09, 29.26, 23.84, 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

4 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) (1H, CH), 2.27 (2H, CH 2 -CH), 1.90 (2H, CH 2 -CH), (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) (1H, CH), 2.26 (2H, CH 2 -CH), 2.03 (2H, CH 2 -CH), (40H, CH 2 ), 0.85 (6H, CH 3 ). 13 C MR (100 MHz, CD 3 Cl, δ): , , , , , , , , , , 58.25, 33.69, 31.76, 29.57, 29.49, 29.40, 29.30, 29.28, 29.21, 26.74, Elementl Anlysis: Cl. (%) for C 37 H 57 3 O 4 : C, 73.11; H, 9.45;, Foun (%): C, 72.74; H, 9.51;, 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

5 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) (2H, OCH 2 ), 3.73 (1H, OH), 1.81 (2H, OCH 2 -CH 2 ), (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): (8H, Ar-H) (8H, OCH 2 ), 1.82 (8H, OCH 2 -CH 2 ), (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) (8H, OCH 2 ), 1.87 (8H, OCH 2 -CH 2 ), (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, Elementl Anlysis: Cl. (%) for C 48 H 80 2 O 8 : C, 70.90; H, 9.92;, Foun (%): C, 70.45; H, 9.78;,

6 Figure S1. The trnsmission eletron mirosopy (TEM) imge of ZrO 2 -supporte AuPs (3 wt%). () O 2 O e () O O e e e Chemil shift (ppm) 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 Chemil shift (ppm) Chemil shift (ppm) Figure S3. 1 H MR spetr of OFL () n OFLA () in CDCl 3. 6

7 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 >98 2 DCM hloroform etone THF nisole MCB >97 8 toluene >99 9 toluene 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

8 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 Chemil shift (ppm) 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

9 M n,gpc (PC) = 4600 g/mol, PDI = 1.50 M n,gpc (PA) = g/mol, PDI = 2.63 M n,gpc (PB) = 4100 g/mol, PDI = 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/ / / / / / / / / / / 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

10 Figure S9. The FT-IR spetr of isnitroromti monomers (A, B n C) n orresponing polymers (PAs, PBs n PCs) with ifferent retion time. () () Chemil shift (ppm) 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

11 PB-4h M = [M + ] + : Cl: Foun: [M + ] + -[] m/z 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: Foun: [O] -[O] -[O] -[O] [M + H] [M + O] + [M + ] + [M + K] m/z photoegrtion prout m/z 11

12 Figure S11. MALDI-TOF-MS spetr of PBs n PCs t ifferent retion time. () 1.2 (404 nm) 0 s () 1.0 As s As s 0 s (546 nm) Wvelength (nm) 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

13 As () 1.0 (365 nm) s 35 s As () s 0 s (435 nm) Wvelength (nm) 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 As Fresh 1 st -reyle 2 n -reyle 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

14 REFERECE S1. Blouin,.; Mihu, A.; Leler, M. Av. Mter. 2007, 19,