Electronic Supplementary Material (ESI) for RSC Advances. This journal is © The Royal Society of Chemistry 2014 Thermal-healable and shape memory metallosupramolecular poly(n-butyl acrylate-co-methyl methacrylate) materials Zhenhua Wang, Wenru Fan, Rui Tong, Xili Lu and Hesheng Xia* Supporting Information Experimental section Materials: Acryloyl chloride, N-methyl-1,2-benzenediamine dihydrochloride which were purchased from Best reagent company. Zinc trifluoromethanesulfonate (Zn(OTf) ), europium 2 trifluoromethanesulfonate (Eu(OTf) ) were purchased from Aladdin reagent corporation. 3 Ethylene glycol dimethyl acrylate (EGDMA) was used as received without any treatment. Monomers including methyl methacrylate (MMA), butyl acrylate (BA) were obtained by reduced pressure distillation. Azodiisobutyronitrile (AIBN) was recrystallized from methanol prior to use. Solvents were used as supplied, with the exception of dimethyformamide (DMF), acetone, triethylamine, dichloromethane (DCM) and THF. Acetone and DCM were dried over CaCl and distilled. THF were distilled from metal Na and benzophenone prior to use. 2 Anhydrous DMF was obtained by reduced pressure distillation after dried over CaH . The 2 chain transfer agent (CTA) S,S’-bis(R,R’-dimethylacetic acid) trithiocarbonate was synthesized according to reference. 1 Synthesis of 4-hydroxy-2,6-bis-(1’-methyl-benzimidazolyl)pyridine (compound 1， HO- Mebip) Chelidonic acid and chelidamic acid were synthesized as literature reported.2 Sodium methylate (8.41g, 155.7 mmol) and N-methyl-1,2-benzenediamine dihydrochloride (15.41g, 79 mmol) were dissolved in 250 ml methanol, then the solution was stirred overnight. The brownish red N-methyl-1,2-benzenediamine (NMB) was obtained by filtration and evaporation of solvent in vacuum. Chelidamic acid (7.41 g, 40.5 mmol) and 25 ml H PO 3 4 were then mixed with the remained NMB, the reaction was left to react for 10 h at 205℃. After reaction, the dark blue mixture was poured into 700ml cold water and was stirred to form blue precipitate. After filtration, the precipitate was collected and the filtrate was neutralized by NaOH (5M) until blue precipitate once again occurred. Then the blue precipitates were suspended in 800 ml hot K CO solution (10% wt). The mixture was stirred 2 3 at 90 ℃ until the color of all the solids turned into pink. Next, the mixture was cooled down and was filtered. The obtained pink solids were re-dissolved in a 600 ml hot methanol to form red solution. The solution was cooled and was further neutralized by adding 1.0 M HCl solution dropwise until it turned to dark blue. The product was collected as light gray solids and dried in vacuo. Yield: 9.6 g, 67% 1H NMR (400 MHz, DMSO-d , δ): 4.24 (s, 6H, -NCH ), 7.67 (d, J = 8.0 Hz, 2H, phenyl-H), 6 3 7.75 (d, J = 7.6 Hz, 2H, phenyl-H), 7.79 (s, 2H, phenyl-H), 11.37 (s, OH). 13C NMR (100 MHz, DMSO-d , δ): 32.48 (CH ), 110.70 (Ar)， 112.50, 119.40， 122.33， 6 3 123.08， 137.02， 141.98， 149.84， 150.90， 165.16. g OH e f d N N N N N c b a e f d a b c g 12 11 10 9 8 7 6 5 4 Chemical shift (ppm) Figure S1. 400 MHz 1H NMR spectrum of 1 in DMSO-d 6 200 180 160 140 120 100 80 60 40 Chemical shift (ppm) Figure S5. 100 MHz 13C NMR spectrum of 1 in DMSO-d 6 O a a HOOC O COOH DMSO-d 6 8 7 6 5 4 3 2 Chemical shift (ppm) Figure S2. 400 MHz 1H NMR spectrum of chelidonic acid in DMSO-d 6 b c OH b a HOOC N COOH c a 12 10 8 6 4 2 Chemical shift (ppm) Figure S3. 400 MHz 1H NMR spectrum of chelidamic acid in DMSO-d 6 Synthesis of 2-(2,6-Bis(1-methyl-1H-benzo[d]imidazol-2-yl)pyridin-4-yloxy)- nonan-1-ol (compound 2，BIP-OH) The self-made HO-Mebip or compound 1 (7.5 g, 21.1 mmol) and K CO (12 g, 87.0 mmol) 2 3 were charged into dry THF with stirring to form uniform mixture. Until the color of mixture turned into red, 2-bromoethanol (13.2 g, 105.7 mmol) was added while stirring and refluxed at 85 ℃ for 24h. After removing heat, the solvent was excluded by rotary evaporator. The remained solids were resuspended in boiling toluene and filtered directly from the boiling suspension. The product was recrystallized from toluene. Yield: 6.8 g, 81% 1H NMR (400 MHz, DMSO-d , δ): 3.83 (d, J = 2.4 Hz, 2H, -OCH CH OH), 4.26 (s, 6H, - 6 2 2 NCH ), 4.32 (d, J = 4.0 Hz, 2H, -OCH2-), 7.33 (m, 2H, phenyl-H), 7.37 (m, 2H, phenyl-H), 3 7.70 (d, J = 8.0 Hz, 2H, phenyl-H), 7.78 (d, J = 7.6 Hz, 2H, phenyl-H), 7.92 (s, 2H, phenyl-H). 13C NMR (100 MHz, DMSO-d , δ): 32.51 (CH ), 59.27, 62.83, 70.31, 110.79 (Ar)，111.17, 6 3 119.44, 122.42, 123.21, 141.92, 149.57, 150.90, 165.81. c d e b e a N N f g OH N O h N N water f da bc toluene g h toluene 8 7 6 5 4 3 2 Chemical shift (ppm) Figure S4. 400 MHz 1H NMR spectrum of 2 in DMSO-d 6 200 180 160 140 120 100 80 60 40 Chemical shift (ppm) Figure S5. 100 MHz 13C NMR spectrum of 2 in DMSO-d 6 Synthesis of 2-(2,6-Bis(1-methyl-1H-benzo[d]imidazol-2-yl)pyridin-4-yloxy)nonyl acrylate (compound 3，Mebip-Ac) Compound 2 (6 g, 15.0 mmol), triethylamine (3.4 ml, 24.4 mmol), dichloromethane (600 ml) were charged to a 1 L round bottom flask, then the solution was kept stirring at 0 ℃ for 2h. The acryloyl chloride (2 ml, 24.5 mmol) dissolved in dichloromethane (20 ml) was added into the above solution dropwise and the mixture was left to react for 4h at 0 ℃, then 24h at room temperature. After reaction, the solution was washed and extracted with NaHCO (1% wt) to 3 remove remained reagents. The organic layer was collected, dried over sodium sulfate, filtered, and concentrated in vacuum. The product was collected and was further purified via column chromatography (CH Cl /MeOH). 2 2 Yield: 3.6 g, 51% 1H NMR (400 MHz, CDCl , δ): 4.24 (s, 6H, -NCH ), 4.51 (d, J = 4.4 Hz, 2H, -OCH CH OH), 3 3 2 2 4.59 (d, J = 4.4 Hz, 2H, -OCH2- ), 5.88 (d, J = 10.4 Hz, 2H), 6.23 – 6.11 (m, 2H),6.45 (t, J = 14.8 Hz, 2H), 34 (m, 6H) , 7.87 (d, J = 7.4 Hz, 2H), 7.99 (s, 2H, phenyl-H) ppm. 13C NMR (100 MHz, CDCl , δ): 32.57, 62.25, 66.39, 76.85, 109.98, 111.71, 120.14, 122.88, 3 123.64, 127.90, 131.63, 137.19, 142.45, 150.11, 151.26, 165.90 ppm. c d b e a e j N i k N O f g O h N O N N f a~c d i~k hg 8 7 6 5 4 3 2 Chemical shift (ppm) Figure S6. 400 MHz 1H NMR spectrum of 3 in CDCl 3 200 180 160 140 120 100 80 60 40 Chemical shift (ppm) Figure S7. 100 MHz 13C NMR spectrum of 3 in CDCl 3 Synthesis of copolymer (CP) Butyl acrylate, methyl methacrylate, monomer compound 3, CTA, AIBN were charged into dry DMF (Table S1), then the mixture was reacted at 70 ℃ for 24h under nitrogen. After polymerization, the solution was poured into cold MeOH/H O (v/v 9:1) to obtain polymer 2 precipitate, and then was dried in vacuum at 50℃. CP-3 CP-5 CP-7 8 6 4 2 0 Chemical shift (ppm) Figure S8. 400 MHz 1H NMR spectra of copolymers with 3%, 5%, 7% Mebip respectively in CDCl and the impurities observed at δ~2.9 is little amount of DMF. 3, Table S1. The feeding ratio of monomers and the composition of the final copolymer determined from 1H NMR Sample f f f F F F BA MMA Mebip-Ac BA MMA Mebip-Ac CP-3 64.7 32.3 3 64.4 32.4 3.2 CP-5 63.3 31.7 5 61.9 32.7 5.4 CP-7 61.9 31.1 7 62.6 29.8 7.6 f repesents the feeding ratio of each monomer, F corresponds to the final ratio of each x x monomer in the copolymer (x=BA, MMA, Mebip-Ac). Figure S9. 100 MHz 13C NMR spectra of copolymers with 3%, 5%, 7% Mebip respectively in CDCl . 3 Table S2. Composition of the carbonyl carbon resonances of BA(B) and MMA(M) centered sequences calculated from peak area of 13C NMR spectra. Sample 1 2 3 4 5 6 7 CP-3 0.02 0.12 0.09 0.15 0.26 0.10 0.26 CP-5 0.03 0.15 0.10 0.14 0.24 0.11 0.23 CP-7 0.03 0.10 0.09 0.13 0.26 0.12 0.27 According to the literature3,4, Peak 1 was assigned to MMM triads; peak 2 to MMM, BMM and MMB; peak 4 to MMM, BMM, MMB and BMB; and peak 6 to the BMB triad. Peak 3, 5, and 7 corresponds to the sequences of B-centered MBM, MBB and BBB triad respectively. Synthesis of MSP series and the control samples: Synthesis of the MSP sample : typically, In a 50 mL beaker the desired amount of the self- made copolymer (CP series) was dissolved in chloroform (100mg/ml). The Zn(OTf) in 2 acetonitrile (100 mg/mL) was added into the copolymer solution. The mixture turned into gel