Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2022 Aug 31;144(34):15443-15450.
doi: 10.1021/jacs.2c06446. Epub 2022 Aug 22.

A Crystalline 1D Dynamic Covalent Polymer

Elisabet De Bolòs  1 , Marta Martínez-Abadía  1 , Félix Hernández-Culebras  1 , Alison Haymaker  2   3 , Kyle Swain  2   3 , Karol Strutyński  4 , Benjamin L Weare  5 , Javier Castells-Gil  6 , Natalia M Padial  6 , Carlos Martí-Gastaldo  6 , Andrei N Khlobystov  5   7 , Akinori Saeki  8 , Manuel Melle-Franco  4 , Brent L Nannenga  2   3 , Aurelio Mateo-Alonso  1   9
Affiliations

A Crystalline 1D Dynamic Covalent Polymer

Elisabet De Bolòs et al. J Am Chem Soc. .

Abstract

The synthesis of crystalline one-dimensional polymers provides a fundamental understanding about the structure-property relationship in polymeric materials and allows the preparation of materials with enhanced thermal, mechanical, and conducting properties. However, the synthesis of crystalline one-dimensional polymers remains a challenge because polymers tend to adopt amorphous or semicrystalline phases. Herein, we report the synthesis of a crystalline one-dimensional polymer in solution by dynamic covalent chemistry. The structure of the polymer has been unambiguously confirmed by microcrystal electron diffraction that together with charge transport studies and theoretical calculations show how the π-stacked chains of the polymer generate optimal channels for charge transport.

PubMed Disclaimer

Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
(a) Synthetic route for Bet-P-1. (b) Front and (c) side views of a single chain of Bet-P-1 in the crystal structure. (d) Top and (e) side views of the crystal structure of Bet-P-1 illustrating the packing of the different chains. Double arrow in the panel indicates the distance between the neighboring dibenzotetraazahexacene units. Hydrogens have been omitted for clarity.
Scheme 1
Scheme 1. Synthesis of Precursor 1
Figure 2
Figure 2
(a) Pawley refinement of the experimental diffraction data of Bet-P-1 collected at room temperature. (b) Large field of view 200 kV TEM image of needle-like crystals dispersed on a lacey-carbon-coated grid. (c) HR-TEM image of an individual crystal revealing distinct lattice fringes running along the main axis of the crystal. (d, e) Separation of 1.4 nm between the areas of high contrast indicating aromatic moieties of the polymer forming (011) crystal planes. (f) N2 adsorption and desorption curves for Bet-P-1. (g) FT-IR spectra of p-phenylenediamine, 1, and Bet-P-1. (h) CP/MAS 13C NMR spectrum of Bet-P-1. (i) 1H NMR spectrum of a hydrolyzed Bet-P-1 sample in TFA-d1 showing the signals of dibenzotetraazahexacene 1 and p-phenylenediamine (2) monomers (*indicates solvent residual peak).
Figure 3
Figure 3
(a) UV–vis–NIR electronic absorption spectrum of Bet-P-1. The inset shows the estimated band gap. (b) Calculated band structure of the crystal structure of Bet-P-1. Top views of selected (c) HOCOs and (d) LUCOs of a Bet-P-1 supercell. (e) Side view of the LUCO of a Bet-P-1 supercell. (f) FP-TRMC conductivity transients of Bet-P-1 upon excitation at 355 nm, 9.1 × 1015 photons cm–2 pulse–1.
See this image and copyright information in PMC

References

    1. Agbolaghi S.; Abbaspoor S.; Abbasi F. A comprehensive review on polymer single crystals—From fundamental concepts to applications. Prog. Polym. Sci. 2018, 81, 22–79. 10.1016/j.progpolymsci.2017.11.006. - DOI
    1. Hasegawa M.; Suzuki Y. Four-center type photopolymerization in the solid state: Poly-2,5-distrylpyrazine. J. Polym. Sci., Part B: Polym. Phys. 1967, 5 (9), 813–815. 10.1002/pol.1967.110050915. - DOI
    1. Wegner G. Topochemische Reaktionen von Monomeren mit konjugierten Dreifachbindungen/Tochemical Reactions of Monomers with conjugated triple Bonds: I., Mitt.: Polymerisation von Derivaten des 2.4-Hexadiin-1.6-diols im kristallinen Zustand. Naturforsch. B 1969, 24 (7), 824–832. 10.1515/znb-1969-0708. - DOI
    1. Hasegawa M., Photodimerization and Photopolymerization of Diolefin Crystals. In Advances in Physical Organic Chemistry; Bethell D., Ed. Academic Press, 1995; Vol. 30, pp 117–171.
    1. Matsumoto A.; Tanaka T.; Tsubouchi T.; Tashiro K.; Saragai S.; Nakamoto S. Crystal Engineering for Topochemical Polymerization of Muconic Esters Using Halogen-Halogen and CH/π Interactions as Weak Intermolecular Interactions. J. Am. Chem. Soc. 2002, 124 (30), 8891–8902. 10.1021/ja0205333. - DOI - PubMed