Solution-processable and functionalizable ultra-high molecular weight polymers via topochemical synthesis

Christopher L Anderson^{1

2}, He Li^#^{1

3}, Christopher G Jones^#⁴, Simon J Teat⁵, Nicholas S Settineri^{2

5}, Eric A Dailing¹, Jiatao Liang^{1

2}, Haiyan Mao⁶, Chongqing Yang¹, Liana M Klivansky¹, Xinle Li¹, Jeffrey A Reimer⁶, Hosea M Nelson⁷, Yi Liu^{8

9}

Affiliations

¹ The Molecular Foundry, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, CA, 94720, USA.
² Department of Chemistry, University of California, Berkeley, Berkeley, CA, 94720, USA.
³ Materials Sciences Division, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, CA, 94720, USA.
⁴ Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA, 90095, USA.
⁵ Advanced Light Source, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, CA, 94720, USA.
⁶ Department of Chemical and Biomolecular Engineering, University of California, Berkeley, Berkeley, CA, 94720, USA.
⁷ Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA, 90095, USA. hosea@chem.ucla.edu.
⁸ The Molecular Foundry, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, CA, 94720, USA. yliu@lbl.gov.
⁹ Materials Sciences Division, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, CA, 94720, USA. yliu@lbl.gov.

^# Contributed equally.

PMID: 34819494
PMCID: PMC8613210
DOI: 10.1038/s41467-021-27090-1

Solution-processable and functionalizable ultra-high molecular weight polymers via topochemical synthesis

Christopher L Anderson et al. Nat Commun. 2021.

. 2021 Nov 24;12(1):6818.

doi: 10.1038/s41467-021-27090-1.

Authors

Affiliations

¹ The Molecular Foundry, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, CA, 94720, USA.
² Department of Chemistry, University of California, Berkeley, Berkeley, CA, 94720, USA.
³ Materials Sciences Division, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, CA, 94720, USA.
⁴ Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA, 90095, USA.
⁵ Advanced Light Source, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, CA, 94720, USA.
⁶ Department of Chemical and Biomolecular Engineering, University of California, Berkeley, Berkeley, CA, 94720, USA.
⁷ Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA, 90095, USA. hosea@chem.ucla.edu.
⁸ The Molecular Foundry, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, CA, 94720, USA. yliu@lbl.gov.
⁹ Materials Sciences Division, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, CA, 94720, USA. yliu@lbl.gov.

^# Contributed equally.

PMID: 34819494
PMCID: PMC8613210
DOI: 10.1038/s41467-021-27090-1

Abstract

Topochemical polymerization reactions hold the promise of producing ultra-high molecular weight crystalline polymers. However, the totality of topochemical polymerization reactions has failed to produce ultra-high molecular weight polymers that are both soluble and display variable functionality, which are restrained by the crystal-packing and reactivity requirements on their respective monomers in the solid state. Herein, we demonstrate the topochemical polymerization reaction of a family of para-azaquinodimethane compounds that undergo facile visible light and thermally initiated polymerization in the solid state, allowing for the first determination of a topochemical polymer crystal structure resolved via the cryoelectron microscopy technique of microcrystal electron diffraction. The topochemical polymerization reaction also displays excellent functional group tolerance, accommodating both solubilizing side chains and reactive groups that allow for post-polymerization functionalization. The thus-produced soluble ultra-high molecular weight polymers display superior capacitive energy storage properties. This study overcomes several synthetic and characterization challenges amongst topochemical polymerization reactions, representing a critical step toward their broader application.

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Conflict of interest statement

The author declares no competing interests.

Figures

**Fig. 1. Single-crystal polymerization of a family of AQM ditriflates.**
a The structures of the AQM ditriflates, 1–4, studied herein. Monomers 1–3 underwent topochemical polymerization under the effects of heat and/or light to produce polymers P1–P3. NR: no reaction. b–c Photographs and optical microscope images of vials containing crystals of (b) 1 and (c) P1, showing the typical morphology of crystals. Scale bar: 1 mm. d–f ¹³C-NMR spectra of polymers **P1–**P3. Cross-polarization/magic angle spinning (CP/MAS) solid-state ¹³C-NMR spectra of (d) P1, and (e) P2 (asterisks denote spinning side bands). (f) Solution ¹³C-NMR spectrum of P3 (solvent: CDCl₃). All carbon resonances are annotated by colored circles. The resonances in d–f between 49–53 ppm (red) indicate the presence of the sp³ carbons generated during polymerization, and the CF₃ multiplets (expected ratio of 1:3:3:1, but only the two highest peaks are observed) between 117 and 120 ppm (orange) show that the triflate groups remain intact.

**Fig. 2. Solid-state structures of monomer 2 and polymer P2.**
a X-ray crystal structure of 2 showing molecular structure, and d_CC—the distance between reactive sites of two neighboring molecules. b CryoEM structure of polymer P2 showing the unit cell structure (top), and a dimeric unit (bottom). c Scanning electron microscopy image of crystals of P2 on a TEM grid similar to those used to obtain its structure by cryoEM. Scale bar: 10 μm. d and e Analogous views of the columnar stacks of monomer 2 and the polymeric chains of P2. Atom color scheme: carbon = gray, nitrogen = blue, oxygen = red, sulfur = yellow, fluorine = green, hydrogen = white, magenta balls represent the truncated polymer chain in polymer P2.

**Fig. 3. Optical and thermal interrogation of the topochemical polymerization of AQMs and capacitive energy storage properties of polymer P3.**
a UV-Vis scanning kinetic curves of a film of 1 (gold) as it polymerizes to form P1 (ruby) over the course of roughly eight hours. b and c DSC studies of monomer 3 and the in-situ thermally polymerized P3. b the first heating (gold), and the subsequent cycle (ruby) of 3 as it polymerizes to P3. c multiple heating and cooling cycles (ruby = first four cycles, blue = final cycle) of P3. d Comparative electric displacement-electric field (D-E) loops at 200 MV m^–1 showing the effective K values derived therefrom. e discharged energy density plots as a function of the electric field, showing the superior energy storage properties of P3 against parylene-C and BOPP (BOPP = biaxially oriented polypropylene; error bars represent standard deviations obtained from at least three measurements using different samples).

**Fig. 4. Postpolymerization functionalization of polymer P3 with amines.**
a The synthesis of two amine-functionalized polymers from reacting polymer P3 with primary and secondary amine nucleophiles. b–d ¹H NMR spectra of (b) polymer P3 and its postpolymerization functionalization products, (c) **P3-A** and (d) **P3-B**, showing 37%, and 57% triflate replacement, respectively. All proton resonances are annotated by colored circles.

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References

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Solution-processable and functionalizable ultra-high molecular weight polymers via topochemical synthesis

Affiliations

Solution-processable and functionalizable ultra-high molecular weight polymers via topochemical synthesis

Authors

Affiliations

Abstract

Conflict of interest statement

Figures

References

Grants and funding

LinkOut - more resources

Full Text Sources