Supplementary Figures.

Transcription

1 Supplementry Figures. c c Supplementry Figure 1 13 C NMR spectrum of representtive smple of PCPC in CDCl 3. The polymer ws purified y using DMS/MeH. CH 2 Cl 2 H 2 DMS Supplementry Figure 2 1 H NMR spectrum of the smple from the rection mixture in d6-dms. The copolymeriztion ws performed in dichloromethne with 100% conversion (Tle 1, entry 7). n ' ' Supplementry Figure 3 1 H NMR spectrum of the smple from the rection mixture in CDCl 3. The copolymeriztion ws performed in net epoxide ctlyzed y rc-2/ppnx (Tle 1, entry 8).

2 c c A B Supplementry Figure 4 13 C NMR nlysis of vrious PCPC. The cronyl, methine nd methylene region of (A) highly isotctic PCPC (ee > 99%, tle 1, entry 3) nd (B) tctic PCPC (ee = 0%, tle 1, entry 8). Supplementry Figure 5 Representtive thermolysis curve of PCPC. The polymer ws with >99% ee (Tle 1, entry 3).

3 Supplementry Figure 6 HPLC spectrum of rcemic dienzote resulted from tctic polycrontes (Tle 1, entry 8).

4 Supplementry Figure 7 HPLC spectrum of (S,S)-enriched dienzote resulted from isotctic polycrontes (Tle 1, entry 3).

5 poly(cpc-co-cpc) c Supplementry Figure 8 1 H NMR spectrum of representtive smple of terpolymer in CDCl 3. The polymer resulted from CP/CP/C 2 tepolymeriztion ws purified y using DMS/MeH (Tle 2, entry 3). ' c poly(cpc-co-cpc) ' c' ' c c c' ' c' Supplementry Figure 9 1 H NMR spectrum of the smple from the rection mixture in CDCl 3. The CP/CP/C 2 terpolymeriztion ws performed in net epoxides ctlyzed y (S,S,S,S)-1/PPNX (Tle 2, entry 3) poly(cpc-co-cpc) Supplementry Figure C NMR spectrum of representtive smple of CP/CP/C 2 terpolymer in CDCl 3. The polymer ws purified y using DMS/MeH (Tle 2, entry 3).

6 Supplementry Tles. Supplementry Tle 1 Monomer feed rtio nd the composition of the resulting polymer during CP/CP/C 2 terpolymeriztion Entry f C (mol %) F C (mol %) c The rection ws performed in 20 ml utoclve t 25 C under 2.0 MP C 2 pressure in net epoxide, (S,S,S,S)-1/PPNX/epoxide = 1/2/1000 (molr rtio, X = 2,4-dinitrophenoxide). Cronte linkges of the resulted polycrontes nd the selectivity for polymer formtion re >99% sed on 1 H NMR spectroscopy. In ll rections, the conversions of epoxides were elow 10% to optimize the determintion of the copolymeriztion prmeters. f C is CP mole frctions in feed. c F C is CPC cronte linkges mole frctions in resulting terpolymer sed on 1 H NMR spectroscopy. Supplementry Methods. NMR experiments. 1 H nd 13 C NMR spectrum were recorded on Vrin INVA-400 MHz type ( 1 H, 400 MHz; 13 C, 100 MHz) spectrometer. Their pek frequencies were referenced versus n internl stndrd (TMS) shifts t 0 ppm for 1 H NMR nd ginst the solvent, chloroform-d t 77.0 ppm for 13 C NMR, respectively. Gel permetion chromtogrphy (GPC). Moleculr weights nd moleculr weight distriutions of polymers were determined with PL-GPC 220 high temperture chromtogrph (Polymer Lortories Ltd.) equipped with the HP 1100 series pump from Agilent Technologies. The GPC columns were eluted with DMF t 35 C t 1.00 ml/min. The smple concentrtion ws out 0.1%, nd the injection volume ws 100 μl. The curve ws clirted using monodisperse polystyrene stndrds covering the moleculr weight rge from 580 to D. Differentil scnning clorimetry (DSC). Anlysis of polycronte ws crried out with NETZSCH DSC 206 therml nlyzer. First cycle: from 20 C to 180 C t heting rte of 10

7 K/min, nd from 180 to 20 C t cooling rte of 10 K/min. Second cycle: from 20 to 310 C t heting rte of 10 K/min. Wide ngle X-ry diffrction (WAXD). Powder X-ry diffrction dt were collected on EMPYREAN diffrctometer with Cu KR rdition (λ = Å) over the 2θ rnge of 5-80 o with scn speed of /s nd step size of o t room temperture. The smples were crystllized isothermlly t 180 C for 2 hours nd mesured t room temperture in ir tmosphere. Thermo-grvimetric nlysis (TGA). Thermo-grvimetric nlyses of ll resulted polymers were mesured on Mettler-Toledo TGA/SDTA851e. Synthesis of ctlyst. The colt complexes 1 nd 2 were prepred ccording to the literture method. 1 Ctlyst (S,S,S,S)-1: 1 H NMR (DMS-d6, 400 MHz): δ 1.29 (s, 18H), (m, 12H), 2.71 (s, 6H), (m, 4H), (m, 4H), (m, 2H), (m, 2H), (m, 4H), (m, 6H), 8.05 (s, 2H), (m, 2H), 8.78 (s, 2H); 13 C NMR (DMS-d6, 100 MHz): δ 20.01, 24.09, 29.05, 31.01, 32.45, 33.82, 38.72, 68.65, 69.89, , , , , , , , , , , , , , , , , , , , HRMS (m/z): Clcd. for [C 56 H 61 Co 2 N 6 9 ] + ([1 X] + ): ; found: , Clcd. For [C 50 H 58 Co 2 N 4 4 ] 2+ ([1 2X] 2+ ): ; found: (X = 2, 4-dinitrophenoxide). Anl. Clc. (C 62 H 64 Co 2 N 8 14 ): C, 58.96; H, 5.11; N, 8.87 %. Found: C, 58.48; H, 5.12; N, 8.11 %. Synthesis of coctlyst. The coctlyst PPNX (PPN = is(triphenylphosphine)iminium, X = 2, 4-dinitrophenoxide) ws prepred ccording to the literturemethod. 2 Procedures for the end-cpping rection of polycrontes. The polycrontes (500 mg) ws trnsferred into flsk nd 10 ml DMS ws dded to dissolve the polymer. After the polymer ws dissolved completely, cetic nhydride (0.1 ml) ws dded. The resultnt mixture ws stirred for 24 h t 50 C. After cooling to room temperture, the mixture ws precipitted from methnol. This process ws repeted 3-5 times to completely remove the impurities, nd white polymer ws otined y vcuum-drying. Determintion of enntiomeric purity of polycrontes. The hydrolysis of polycrontes ws pplied s the previously descried y Nozki et l. 3 The determintion of the ee vlue of cyclopentne-1,2-diol ws pplied s the previously descried y Lu et l. 1 The hydrolysis nd derivtion of polycrontes from 3,4-epoxytetrhydrofurn ws pplied s the previously

8 descried y Lu et l. 1 Ph H H NH(q) Ph Cl, Et 3 N THF THF Ph polycrontes trns-1,2-diol trns-dienzote The ee of the dienzotes ws determined y HPLC using chirl column (DALCEL, CHIRALCEL J-H, hexne/ i PrH = 90/10, flow rte = 1.0 ml/min, 254 nm, t R = 12.7 min for (S,S)-enntiomer nd 26.1 min for (R,R)-enntiomer) (Supplementry Figs S6 nd S7). Procedures for terpolymerizing CP, CP with C 2. In predried 20 ml utoclve equipped with mgnetic stirrer, ctlyst (S,S,S,S)-1 (0.030 mmol, 1 equiv), PPNX (X = 2,4-dinitrophenoxide, mmol, 2 equiv), were dissolved in CP (15 mmol, 500 equiv) nd CP (15 mmol, 500 equiv) (the molr rtio of CP nd CP ws vried with different experiments) in n rgon tmosphere. After C 2 ws introduced, the rection mixture ws stirred t 25 C for the llotted time. Then C 2 ws relesed, smll mount of the resultnt mixture ws removed from the utoclve for 1 H NMR nlysis to quntittively give the proportion of CPC nd CPC crontes units. The crude polymer ws dissolved in 10 ml DMS nd precipitted from methnol. This process ws repeted 3-5 times to completely remove the ctlyst, nd white polymer ws otined y vcuum-drying. Supplementry References. 1. Liu, Y., Ren, W. M., Liu, J. & Lu, X. B. Asymmetric copolymeriztion of C 2 with meso-epoxides medited y dinucler colt(iii) complexes: unprecedented enntioselectivity nd ctivity. Angew. Chem. Int. Ed. 52, (2013). 2. Wu, G. P., Wei, S. H., Lu, X. B., Ren, W. M. & Drensourg, D. J. Highly selective synthesis of C 2 copolymer from styrene oxide. Mcromolecules 43, (2010). 3. Nozki, K., Nkno, K. & Hiym, T. pticlly ctive polycrontes: symmetric lternting copolymeriztion of cyclohexene oxide nd cron dioxide. J. Am. Chem. Soc. 121, (1999).