Abstract
Single-crystal-to-single-crystal (SCSC) polymerization offers an effective protocol for the environmentally friendly preparation of polymer single crystals (PSCs) with extremely high crystallinity and very large molecular weights. Single-crystal X-ray diffraction (SCXRD) serves as a powerful technique for the in-depth characterization of their structures at a molecular level. Hence, a fundamental understanding of the structure-property relationships of PSCs is within our reach. Most of the reported PSCs, however, suffer from poor solubility, a property which hampers their post-functionalization and solution processability when it comes to practical applications. Here, we report soluble and processable PSCs with rigid polycationic backbones by taking advantage of an ultraviolet-induced topochemical polymerization from an elaborately designed monomer that results in a multitude of photoinduced [2 + 2] cycloadditions. The high crystallinity and excellent solubility of the resulting polymeric crystals enable their characterization both in the solid state by X-ray crystallography and electron microscopy and in the solution phase by NMR spectroscopy. The topochemical polymerization follows first-order reaction kinetics to a first approximation. Post-functionalization of the PSCs by anion exchange renders them super-hydrophobic materials for water purification. Solution processability endows PSCs with excellent gel-like rheological properties. This research represents a major step towards the controlled synthesis and full characterization of soluble single-crystalline polymers, which may find application in the fabrication of PSCs with many different functions.
Original language | English (US) |
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Pages (from-to) | 13223-13231 |
Number of pages | 9 |
Journal | Journal of the American Chemical Society |
Volume | 145 |
Issue number | 24 |
DOIs | |
State | Published - Jun 21 2023 |
Funding
Y.L., X.-R.G., D.-C.W., and Q.-H.G. gratefully acknowledge the financial support from the National Natural Science Foundation of China (22193020 and 22193022), the Starry Night Science Fund of the ZJU Shanghai Institute for Advanced Study (SN-ZJU-SIAS-006), Zhejiang University (ZJU), and the ZJU-Hangzhou Global Scientific and Technological Innovation Center. J.F.S. acknowledges support from Northwestern University.
ASJC Scopus subject areas
- General Chemistry
- Biochemistry
- Catalysis
- Colloid and Surface Chemistry
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CCDC 2223226: Experimental Crystal Structure Determination
Liu, Y. (Contributor), Guan, X.-R. (Contributor), Wang, D.-C. (Contributor), Stoddart, J. F. (Contributor) & Guo, Q.-H. (Contributor), Cambridge Crystallographic Data Centre, 2023
DOI: 10.5517/ccdc.csd.cc2dmfzg, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc2dmfzg&sid=DataCite
Dataset
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CCDC 2223227: Experimental Crystal Structure Determination
Liu, Y. (Contributor), Guan, X.-R. (Contributor), Wang, D.-C. (Contributor), Stoddart, J. F. (Contributor) & Guo, Q.-H. (Contributor), Cambridge Crystallographic Data Centre, 2023
DOI: 10.5517/ccdc.csd.cc2dmg0j, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc2dmg0j&sid=DataCite
Dataset