SUPPLEMENTARY INFORMATION

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1 DOI: /NCHEM.1576 Highly ordered alignment of a vinyl polymer by host guest cross- polymerization Gaetano Distefano, Hirohito Suzuki, Masahiko Tsujimoto, Seiji Isoda, Silvia Bracco, Angiolina Comotti, Piero Sozzani, Takashi Uemura,* and Susumu Kitagawa* * To whom corresponding should be addressed. E- mail: uemura@sbchem.kyoto- u.ac.jp; kitagawa@icems.kyoto- u.ac.jp NATURE CHEMISTRY 1

2 Table of Contents Experimental methods Supplementary Figure S1: XRPD patterns of 1 x. Supplementary Figure S2: 1 H NMR spectra of 1 x dissolved in D 2 O/Na 2 - EDTA. Supplementary Figure S3: Thermogravimetric analyses of 1 x, 1 x St, and 1 x PSt. Supplementary Table S1: Summary of St polymerization in 1 x. Supplementary Figure S4: Molecular dynamics simulation of Supplementary Figure S5: XRPD patterns of 1 x PSt. Supplementary Figure S6: 1 H NMR of 1 x and relative 1 x PSt dissolved in D 2 O/Na 2 - EDTA. Supplementary Figure S7: FTIR spectra of PSt. Supplementary Figure S8: Solid- state NMR spectra of PSt obtained from Supplementary Figure S9: Differential scanning calorimetry data of PSt. Supplementary Table S2: Summary of glass transition temperatures for PSt. Supplementary Figure S10: SEM- EDX analysis of , PSt, and isolated PSt. Supplementary Figure S11: N 2 adsorption isotherms on PSt. Supplementary Figure S12: XRPD patterns of PSt from and possible contamination sources. Supplementary Figure S13: XRPD pattern of PSt obtained from Supplementary Figure S14: SEM micrographs of , PSt, and PSt recovered from Supplementary Figure S15: SEM- EDX analysis of PSt from prior and after acidification. Supplementary Figure S16: FTIR spectra of PSt from prior and after acidification. Supplementary Figure S17: XRPD patterns of PSt from prior and after acidification. Supplementary Figure S18: TEM images of PSt obtained from Supplementary Figure S19: XRPD patterns of PSt after solvent and thermal treatments. Supplementary Figure S20: XRPD patterns of PSt from recorded at variable temperature. Supplementary Figure S21: Thermogravimetric analysis of PSt with different cross- linker ratio. Supplementary Figure S22: Thermogravimetric analysis of ordered and amorphous PSt samples. Supplementary Figure S23: XRPD patterns of PSt before and after thermal treatment at 500 C. Supplementary Figure S24: XRPD patterns of 1 x PMMA. Supplementary Figure S25: Thermogravimetric analysis of 1 x MMA and 1 x PMMA. Supplementary Table S3: Summary of MMA polymerization in 1 x. Supplementary Figure S26: XRPD patterns of PMMA obtained from 1 x. NATURE CHEMISTRY 2

3 Experimental methods X- ray powder diffraction (XRPD) experiments were carried out using Rigaku RINT 2000 Ultima diffractometer operating with Bragg- Brentano geometry with fixed sample- holder, using monochromated Cu Kα radiation at scanning speeds of 6 deg. min - 1 or 1 deg. min - 1, for PCPs/nanocomposites and host- guest crosslinked polymers, respectively. 1 H NMR spectra were obtained using a JEOL A- 500 spectrometer operating at 500 MHz using 90 pulse and 5s recycle delay. Thermogravimetric analysis (TGA) were performed using a Rigaku Instrument Thermo plus TG 8120 TGA system equipped with auto- sampler mg of sample were put in 40µl aluminum pan and then scanned from room temperature to 500 C (heating rate: 10 K/min) under nitrogen atmosphere (N 2 flow: 50 ml min - 1 ). In the case of host- guest cross- linked PSt, the sample was brought to the final temperature of 700 C using platinum pans, instead. Monomer content in PCP monomer and PCP polymer adducts was estimated by the weight loss at 200 C. Monomer:DVTPA molar ratio in polymeric products was estimated as follows. TGA measurements on 1 x polymer and 1 x monomer allowed the determination of monomer conversion and the weight fraction of reacted monomer with respect to 1 x polymer nanocomposite (A). The weight fraction of reacted DVTP with respect to 1 x polymer nanocomposite (B) was calculated employing the results from 1 H NMR (Fig. S6). Given the general brute formula for 1 x, [Cu(DVTP) x (terephthalate) 1- x triethylenediamine 0.5 ] n, and being y the fraction of grafted DVTP (0<y<x), it is possible to determine the contribution of reacted DVTP to the PCP molecular weight (χ) by χ = (y m.m.r. DVTP ) / m.m.r. PCP And therefore B = χ K/100; where K is the wt% of PCP in PCP polymer nanocomposite, deduced from TGA. Then DVTP wt fraction in cross- polymer = B / (A+B) while reacted monomer wt fraction in cross- polymer = A / (A+B). Conversion to mol ratios is obtained taking account of monomer and DVTP molecular weights. SEM- energy- dispersive X- ray (EDX) measurements were conducted by using a JEOL JED detector in a JEOL JSM at an accelerating voltage of 15 kv. The molar ratio of DVTPA incorporation x was determined by means of the 1 H NMR integrated aromatic signals of the terephthalate and DVTP anions. For this purpose a tip of a spatula of PCP was decomposed in a D 2 O/Na 2 - EDTA solution (0.05M) and then analyzed. Paramagnetic Cu 2+ ions do not disturb the NMR characterization since completely sequestrated by the Cu- EDTA complex. Differential scanning calorimetry (DSC) was carried out with Seiko Instruments DSC 6220 under N 2 atmosphere and 20 K min - 1 heating rate. Determination of glass transition temperature (Tg) was performed on second heating ramp after a heating- cooling thermal cycle. The infrared spectra were measured employing a Thermo Scientific Nicolet is5. Molecular dynamics (MD) simulations were performed using the Materials Studio Modeling v4.4 software package (Accelrys Inc., San Diego, CA, USA) using the Universal Force Field, as implemented in the Forcite module. The charges were dealt with by charge equilibration method in this system. The initial structure of was generated based on the X- ray crystal structure of pure 1. The quench NATURE CHEMISTRY 3

4 dynamics with the optimized structures were conducted at 1298 K and then MD calculations were carried out at 298 K for 1000 ps under NVT conditions. Sorption isotherms of N 2 were measured with a Quantachrome Autosorb- 1 volumetric adsorption instrument. N 2 gas of high purity ( %) was used. Prior to the adsorption measurements, the sample was treated under reduced pressure (<10-2 Pa) at 343 K for 5 h. Density of PSt was measured by helium pycnometry using MicroUltraPycnometer 1200e (Quantachrome) at 298 K. TEM observation was performed with a TEM/STEM of JEM- 2200FS operated at 200 kv. For dark- filed TEM observation, a cryogenic TEM (JEM- 2100F(G5) operated at 200 kv) was used. In dark- filed TEM imaging, one or a few particular diffraction spots were taken for the image formation into an objective aperture, so that bright contrasts of particles indicate the crystalline domains giving the particular crystalline diffractions captured in an objective aperture. In the present case, the 4.9 Å diffraction spots were captured in an aperture. Quantitative 1 H MAS NMR measurements were performed with a Bruker Avance III 600 MHz instrument operating at 14.1 T, using a recycle delay of 20 s. A MAS Bruker probe head was used with 2.5 mm ZrO 2 rotors spinning at 35 khz. 13 C solid- state NMR spectra were run on a Bruker Avance 300 instrument operating at a static field of 7.04 T equipped with 4 mm double resonance MAS probe. The samples were spun at the magic angle at 15 khz, and RAMP- CP transfer of magnetization was applied. The 90 pulse for proton was 2.9 μs. Phase- modulated Lee- Goldburg (PMLG) heteronuclear 1 H- 13 C correlation (HETCOR) experiments coupled with 15 khz magic angle spinning allowed the recording of 2- D spectra with high resolution both in the hydrogen and in the carbon dimensions. Narrow hydrogen resonances, with line widths in the order of 1-2 ppm, were obtained with homonuclear decoupling during t1; this resolution permits a sufficiently accurate determination of the proton species present in the system. PMLG 1 H- 13 C HETCOR spectra were run with a LG period of 18.9 μs. Efficient transfer of magnetization to the carbon nuclei was performed using the RAMP- CP sequence. Quadrature detection in t1 was achieved by the time proportional phase increments method (TPPI). Carbon signals were acquired during t2 under proton decoupling applying the two- pulse phase modulation (TPPM) scheme. NATURE CHEMISTRY 4

5 a b Supplementary Figure S1. (a) Comparison between XRPD of [Cu(DVTP) x (terephthalate) 1- x triethylenediamine 0.5 ] n (1 x ). Mixed ligand PCPs are isostructural to 1 0 in all cases, indicating that functionalized DVTP ligand is incorporated in the metal- organic architecture without perturbing its arrangement. Instead, complete substitution of DVTP ligand in 1 framework leads to [Cu(DVTP)triethylenediamine 0.5 ] n, 1 1 which has poor crystallinity (b). NATURE CHEMISTRY 5

6 Supplementary Figure S2. 1 H NMR spectra of 1 x dissolved in D 2 O/Na 2 - EDTA (vinyl and aromatic region). Amount of DVTP in the PCPs is measured as the ratio between the integrated aromatic terephthalate signal (4H, 7.70 ppm) and those of DVTP (both aromatic and vinyl). Asterisk designates a DMF impurity. NATURE CHEMISTRY 6

7 Supplementary Figure S3. Thermogravimetric analyses of 1 x (dashed line), 1 x St (black line), and 1 x PSt. (red line). Mixed ligand PCPs are thermally stable up to 250 C in all cases and comparable to 1 0. Thermal desorption of styrene monomer adsorbed in the PCP nanochannels is detected as weight loss having endpoint below 200 C. The degree of monomer conversion is calculated by the difference in monomer release in PCP monomer and PCP polymer adducts due to the formation of non- volatile macromolecular species. NATURE CHEMISTRY 7

8 Supplementary Table S1 Summary of data from TGA and 1 H NMR experiments on polymerization of St in 1 x DVTPA provided in PCP synthesis [mol fraction] DVTP content in 1 x [mol fraction] St content in 1 x St [% wt] St content in 1 x PSt [% wt] St conversion [%] DVTP conversion [%] PSt in 1 x PSt (A) [% wt] Reacted DVTP in 1 x [% wt] PCP in 1 x PSt, (K) [% wt] Reacted DVTP in 1 x PSt, (B) [% wt] DVTPA : St mol ratio in cross- polymer : : : : : : : 77 NATURE CHEMISTRY 8

a) b) Supplementary Figure S4. Molecular dynamics simulation of 1 0.025. (a) Side view of nano- channels developing along the crystalline c axis.

9 a) b) Supplementary Figure S4. Molecular dynamics simulation of (a) Side view of nano- channels developing along the crystalline c axis. (b) Front view evidencing the square cross- section of 1 architecture and the position of divinyl moieties, leaning on opposite sides of the nano- channel walls (DVTP ligand highlighted in green). NATURE CHEMISTRY 9

10 Supplementary Figure S5. XRPD profiles of 1 x PSt nanocomposites showing how PCP architecture is still retained after styrene soaking and polymerization. NATURE CHEMISTRY 10

11 Supplementary Figure S6. 1 H NMR of D 2 O/Na 2 - EDTA solutions of 1 x and relative 1 x PSt nanocomposites in the aromatic and vinyl region. Spectra are normalized on terephthalate intensity for comparison. Signals from DVTP ligand are depressed due to grafting of the crosslinker to insoluble PSt. NATURE CHEMISTRY 11

12 Supplementary Figure S7. ATR FTIR spectra of host- guest cross polymerized poly(st- co- DVTPA) polymerized in 1 x (x=0.01, 0.03, 0.05 and 0.06), of poly(st) obtained from 1 0 (bottom) and solution- polymerized poly(st 90 - co- DVTPA 10 ) (top). NATURE CHEMISTRY 12

13 a b Supplementary Figure S8. (a)- 1 H MAS NMR spectrum of PSt from recorded at 14 T and a spinning frequency of 35 khz. In the 1 H MAS NMR spectrum recorded at 600 MHz and 35 khz spinning speed we can recognize the hydrogens of the carboxylic acid at about 13 ppm indicating that the carboxylic groups are protonated. (b) 1D 13 C CP MAS NMR spectrum of PSt from recorded with a short contact time of 50 µs highlighting the carbon atoms covalently bonded to hydrogens (spinning speed of 12.5 khz). NATURE CHEMISTRY 13

14 Supplementary Figure S9. Differential scanning calorimetry of host- guest poly(st- co- DVTPA) polymerized in 1 x (x=0, 0.01, 0.03, 0.04, 0.05 and 0.06) and of solution- polymerized poly(st 90 - co- DVTPA 10 ). Supplementary Table S2 Summary of glass transition temperatures for cross- polymerized poly(st- co- DVTPA) with different cross- linker amounts. PCP Polymer composition Tg [ C] 1 0 Poly(St) Poly(St 99 - co- DVTPA 1 ) Poly(St 97 - co- DVTPA 3 ) Poly(St 94 - co- DVTPA 6 ) Poly(St 92 - co- DVTPA 8 ) Poly(St 93 - co- DVTPA 7 ) NATURE CHEMISTRY 14

a b c Supplementary Figure S10. SEM- EDX analysis of (a) 1 0.06, (b) 1 0.06 PSt, and (c) isolated host- guest cross- polymerized PSt.

15 a b c Supplementary Figure S10. SEM- EDX analysis of (a) , (b) PSt, and (c) isolated host- guest cross- polymerized PSt. Copper map demonstrate the complete removal of PCP architecture during polymer recovery. Scale bars equal 5µm. NATURE CHEMISTRY 15

16 DOI: /NCHEM.1576 Supplementary Figure S11. N2 adsorption isotherms on PSt obtained from 10.01(filled circles) and solution polymerized poly(st- co- DVTPA) (open circles) at 77 K. The inset shows pore size distribution of PSt prepared in using Barrett Joyner Halenda (BJH) analysis, determined from N2 adsorption profile, which reveals the presence of meso and macroporous voids in the structure. 16 NATURE CHEMISTRY

17 Supplementary Figure S12. XRPD profiles of PSt from and possible contamination sources: 1 0, terephthalic acid, and Na 2 - EDTA. Indeed, none shows unique reflection at 2θ = Supplementary Figure S13. XRPD profile of PSt obtained from , which did not show a diffraction peak for ordered chain alignment. NATURE CHEMISTRY 17

a b c Supplementary Figure S14. SEM micrographs of (a) 1 0.10, (b) 1 0.10 PSt nanocomposite, and (c) recovered PSt cross- polymerized in 1 0.10. Albeit XRPD of PCP matrix and nanocomposite are acceptable (Supplementary Figs.

18 a b c Supplementary Figure S14. SEM micrographs of (a) , (b) PSt nanocomposite, and (c) recovered PSt cross- polymerized in Albeit XRPD of PCP matrix and nanocomposite are acceptable (Supplementary Figs. S1 and S5), single crystals are not recognizable: agglomerated nanometer sized powders are found instead, leading to conglomerated PSt after polymer isolation. NATURE CHEMISTRY 18

a b Supplementary Figure S15. SEM- EDX analysis of PSt from 1 0.06 prior (a) and after (b) acidification.

19 a b Supplementary Figure S15. SEM- EDX analysis of PSt from prior (a) and after (b) acidification. As shown by the comparison of sodium maps, acidification removes Na cations from the polymeric material, yielding free carboxylic acid. Scale bars equal 20µm. a b Supplementary Figure S16. ATR- FTIR spectra of PSt from (a) prior and (b) after acidification. Upon acidification and washing with distilled water, sodium carboxylate groups are converted into acidic groups as shown by the shift of the C=O stretching signal. Moreover, the two bands at 1203 cm - 1 and 1148 cm - 1 (thought as sensitive to chain packing and conformation) appear (see main text). NATURE CHEMISTRY 19

a b c Supplementary Figure S17. (a) XRPD of PSt from 1 0.06 prior and after acidification.

appearance of the sharp peak at 2θ = 18.0.

20 a b c Supplementary Figure S17. (a) XRPD of PSt from prior and after acidification. Notice how the amorphous band centered at 2θ = 20 is suppressed after acid treatment, with the appearance of the sharp peak at 2θ = Displacement of hindering Na + cations (b) improves the chain packing (c) and sample crystallinity (grey: C, white: H, red: O and cyan: Na). NATURE CHEMISTRY 20

DOI: 10.1038/NCHEM.1576 Supplementary Figure S18. (a) HR- TEM image of PSt obtained from 10.06. In this measurement, the observed size of domain presenting the lattice fringes was about 20-30 nm.

21 DOI: /NCHEM.1576 Supplementary Figure S18. (a) HR- TEM image of PSt obtained from In this measurement, the observed size of domain presenting the lattice fringes was about nm. Although long- range ordering of PSt chains was surely observable, the resulting TEM images were severely deteriorated because of radiation damages and deformation of samples by a heavy electron dosage at such high magnifications. (b) and (c) Dark- field TEM images of PSt obtained from The dark- field TEM observation was conducted at liquid- helium temperature with a cryogenic TEM operated at 200 kv so as to minimize the radiation damage of the samples. Since dark- filed TEM images can be taken at much lower magnification than the case of high resolution measurements, it is possible to avoid image deterioration originated from radiation damage. In this work, PSt crystalline particles synthesized by the cross- polymerization were supported on a holey plastic film. Among them, some particles exhibited bright contrasts corresponding to the particularly oriented crystalline domains of the aligned PSt chains in the submicron range, suggesting that the crystalline domain ranges extensively over the single particles. 21 NATURE CHEMISTRY

22 Supplementary Figure S19. XRPD profiles of host- guest cross- polymerized PSt (from and ) after solvent and thermal treatments. Diffraction peak at 2θ = 18.0 demonstrates the resistance of chain alignment against chaotropic stimuli. NATURE CHEMISTRY 22

23 a b Supplementary Figure S20. (a) Sequence of XRPD profiles of PSt from recorded at variable temperature (from 50 C to 190 C). With increased temperature, peak position shifts towards larger inter- plane distances in accordance with thermal expansion. The crystalline peak is present above the glass transition temperature for PSt (112 C). Inter- chain expansion is fully reversible, as seen from room temperature XRPD profile recorded after cooling. (b) Plot of inter- plane distance vs. temperature showing linear proportionality. Temperature [ C] Peak position [ ] d [Å] NATURE CHEMISTRY 23

Instead, decomposition of cross- linked PSt produces primary char which is then decomposed around 600 C. Increase in cross- linker density leads to increase in primary char residue.

24 Supplementary Figure S21. Thermogravimetric analysis of host- guest cross polymerized poly(st- co- DVTPA) obtained in 1 x (x=0.01, 0.03, 0.04, 0.05 and 0.06) and poly(st) obtained from non- functionalized 1 0. In absence of crosslinker, thermal degradation occurs via monomer unzipping quantitatively above 400 C. Instead, decomposition of cross- linked PSt produces primary char which is then decomposed around 600 C. Increase in cross- linker density leads to increase in primary char residue. Supplementary Figure S22. Thermogravimetric analysis of host- guest cross- polymerized PSt obtained in after HCl treatment (full green), PSt from prior to HCl treatment (poly(st- co- DVTP- Na) form, full black) and solution polymerized poly(st 90 - co- DVTPA 10 ) (dashed black). The pseudo- crystalline polymer exhibits enhanced thermal stability compared to more disordered chains situations. NATURE CHEMISTRY 24

25 Supplementary Figure S23. XRPD profiles of PSt from before and after thermal treatment at 500 C under N 2 atmosphere. The material treated at high temperatures exhibits the persistence of the diffraction peak with shift to slightly smaller d- spacing, indicating remarkable thermal stability of the pseudo- crystalline arrangement. Supplementary Figure S24. XRPD profiles of 1 x PMMA nanocomposites (x=0, 0.01, 0.03 and 0.05) showing how PCP architecture is still retained after MMA soaking and polymerization. NATURE CHEMISTRY 25

26 Supplementary Figure S25. Thermogravimetric analysis of 1 x MMA (black line) and 1 x PMMA. (red line). Supplementary Table S3 Summary of data from TGA and 1 H NMR experiments on PMMA polymerization in 1 x DVTPA provided in PCP synthesis [mol fraction] DVTP content in 1 x [mol fraction] MMA content in 1 x MMA [% wt] MMA content in 1 x PMMA [% wt] MMA conversion [%] NATURE CHEMISTRY 26

27 Supplementary Figure S26. XRPD profiles of PMMA from 1 x (x=0, 0.01, 0.03 and 0.05). Crystalline peak at 2θ = 18.0 appears also in case of host- guest cross- polymerized poly(mma- co- DVTPA), demonstrating the generality of ordered chain alignment. NATURE CHEMISTRY 27

Supplementary Information T. Ebert, a A. Wollbrink, b A. Seifert, a R. John, a and S. Spange a

Electronic Supplementary Material (ESI for Polymer Chemistry. This journal is The Royal Society of Chemistry Please do 216 not adjust margins ARTICLE Supplementary Information T. Ebert, a A. Wollbrink,