Precision Topochemical Synthesis of Single-crystal Polymers

WANG Xiu-dong; LI Lin-lin; WANG Hui; ZHAO Ying-jie; LIU Hui

doi:10.14028/j.cnki.1003-3726.2026.26.129

您当前的位置：

首页 >

文章列表页 >

Precision Topochemical Synthesis of Single-crystal Polymers

更新时间：2026-07-27

- Precision Topochemical Synthesis of Single-crystal Polymers
- Polymer Bulletin Vol. 39, Issue 8, Pages: 1361-1372(2026)
- 作者机构：
  
  青岛科技大学高分子科学与工程学院高性能有机光学聚合物与先进制造技术全国重点实验室　青岛 266042
  山东省产品质量检验研究院　济南 250102
  国家市场监督管理总局技术创新中心(绿色包装评价)　济南 250102
- 作者简介：
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2026.26.129
  CLC：
- Received：06 March 2026，
  
  Accepted：20 May 2026，
  
  Online First：10 July 2026，
  
  Published：20 August 2026
- 稿件说明：
移动端阅览
王修东, 李林林, 王惠, 赵英杰, 刘辉. 单晶聚合物的精准拓扑合成. 高分子通报, 2026, 39(8), 1361–1372.

Wang, X. D.; Li, L. L.; Wang, H.; Zhao, Y. J.; Liu, H. Precision topochemical synthesis of single-crystal polymers. Polym. Bull. (in Chinese), 2026, 39(8), 1361–1372.
王修东, 李林林, 王惠, 赵英杰, 刘辉. 单晶聚合物的精准拓扑合成. 高分子通报, 2026, 39(8), 1361–1372. DOI： 10.14028/j.cnki.1003-3726.2026.26.129.

Wang, X. D.; Li, L. L.; Wang, H.; Zhao, Y. J.; Liu, H. Precision topochemical synthesis of single-crystal polymers. Polym. Bull. (in Chinese), 2026, 39(8), 1361–1372. DOI： 10.14028/j.cnki.1003-3726.2026.26.129.

摘要

近年来，具有明确原子级别结构的单晶聚合物引起了广泛关注。精确的结构信息对理解聚合物排列方式、分子间相互作用、结构—性能关系至关重要。目前，制备大尺寸单晶聚合物的方法仍然是高分子合成领域面临的关键挑战。拓扑化学聚合因其无溶剂、高区域选择性等特点，能实现单体单晶到聚合物单晶的直接转化，是制备单晶聚合物的有效途径。本综述系统总结了近年来拓扑化学聚合在构筑单晶聚合物方面的研究进展，并基于反应类型对典型体系进行了归纳，重点讨论了如[2+2]环加成、[4+4]环加成、二炔/三炔聚合及其他晶格约束反应的结构特征、反应条件及适用范围。此外，汇总了具有明确结构信息的代表性单晶聚合物实例，同时对单晶聚合物的潜在应用领域、发展机遇和挑战进行了简单探讨。

Abstract

In recent years

single-crystal polymers with well-defined atomic-level structures have attracted considerable attention. Precise structural information is crucial for understanding polymer arrangement

intermolecular interactions

and structure-property relationships. The preparation of large single-crystal polymers remains a key challenge in polymer synthesis. Topochemical polymerization

owing to its solvent-free nature and high regioselectivity

enables the direct conversion of monomer crystals to polymer single crystals

providing an effective approach for the preparation of single-crystal polymers. This review systematically summarizes recent advances in topochemical polymerization for constructing single-crystal polymers

categorizing typical systems based on reaction types. The structural features

reaction conditions

and applicability of reactions such as [2+2] cycloaddition

[4+4] cycloaddition

diyne/triyne polymerization

and other lattice-constrained reactions are discussed in detail. Additionally

this paper presents a summary of representative single-crystal polymer examples with well-defined structural information and briefly explores the potential application fields

development opportunities

and challenges of single-crystal polymers.

关键词

Keywords

references

Staudinger, H . Über polymerisation . Ber. Dtsch. Chem. Ges. A/B , 1920 , 53 ( 6 ), 1073 – 1085 .

Staudinger, H. ; Fritschi, J . Über isopren und kautschuk. 5. Mitteilung. Über die hydrierung des kautschuks und über seine konstitution . Helv. Chim. Acta , 1922 , 5 ( 5 ), 785 – 806 .

燕青青 , 姚奕帆 , 董焕丽 , 胡文平 . 拓扑化学聚合在高分子晶体材料制备中的应用 . 中国科学(化学) , 2016 , 46 ( 10 ), 1007 – 1022 .

Hema, K. ; Ravi, A. ; Raju, C. ; Pathan, J. R. ; Rai, R. ; Sureshan, K. M . Topochemical polymerizations for the solid-state synthesis of organic polymers . Chem. Soc. Rev. , 2021 , 50 ( 6 ), 4062 – 4099 .

Schmidt, G. M. J . Photodimerization in the solid state . Pure Appl. Chem. , 1971 , 27 ( 4 ), 647 – 678 .

Yelgaonkar, S. P. ; Campillo-Alvarado, G. ; MacGillivray, L. R . Phototriggered guest release from a nonporous organic crystal: remarkable single-crystal-to-single-crystal transformation of a binary cocrystal solvate to a ternary cocrystal . J. Am. Chem. Soc. , 2020 , 142 ( 49 ), 20772 – 20777 .

Ali Al-Mohsin, H. ; AlMousa, A. ; Oladepo, S. A. ; Jalilov, A. S. ; Fettouhi, M. ; Peedikakkal, A. M. P . Single-crystal-to-single-crystal transformation of hydrogen-bonded triple-stranded ladder coordination polymer via photodimerization reaction . Inorg. Chem. , 2019 , 58 ( 15 ), 10167 – 10173 .

Huang, S. L. ; Andy Hor, T. S. ; Jin, G. X . Photodriven single-crystal-to-single-crystal transformation . Coord. Chem. Rev. , 2017 , 346 , 112 – 122 .

Devic, T. ; Batail, P. ; Avarvari, N . [2+2] Photocyclization in a single-crystal-to-single-crystal transformation of a TTF-amido-pyridine . Chem. Commun. , 2004 , ( 13 ), 1538 – 1539 .

Chu, Q. L. ; Swenson, D. C. ; MacGillivray, L. R . A single-crystal-to-single-crystal transformation mediated by argentophilic forces converts a finite metal complex into an infinite coordination network . Angew. Chem. Int. Ed. , 2005 , 44 ( 23 ), 3569 – 3572 .

Garai, M. ; Santra, R. ; Biradha, K . Tunable plastic films of a crystalline polymer by single-crystal-to-single-crystal photopolymerization of a diene: self-templating and shock-absorbing two-dimensional hydrogen-bonding layers . Angew. Chem. Int. Ed. , 2013 , 52 ( 21 ), 5548 – 5551 .

Turowska-Tyrk, I. ; Trzop, E . Monitoring structural transformations in crystals. 6. The [4+4] photodimerization of 9-methylanthracene . Acta Crystallogr. Sect. B Struct. Sci. , 2003 , 59 ( 6 ), 779 – 786 .

Kissel, P. ; Murray, D. J. ; Wulftange, W. J. ; Catalano, V. J. ; King, B. T . A nanoporous two-dimensional polymer by single-crystal-to-single-crystal photo-polymerization . Nat. Chem. , 2014 , 6 ( 9 ), 774 – 778 .

Servalli, M. ; Trapp, N. ; Schlüter, A. D . Single-crystal-to-single-crystal (SCSC) linear polymerization of a desymmetrized anthraphane . Chem. , 2018 , 24 ( 56 ), 15003 – 15012 .

Yu, Q. ; Li, M. M. ; Gao, J. ; Xu, P. X. ; Chen, Q. Z. ; Xing, D. ; Yan, J. ; Zaworotko, M. J. ; Xu, J. ; Chen, Y. ; Cheng, P. ; Zhang, Z. J . Fabrication of large single crystals for platinum-based linear polymers with controlled-release and photoactuator performance . Angew. Chem. Int. Ed. , 2019 , 58 ( 51 ), 18634 – 18640 .

Tanaka, T. ; Matsumoto, A . First disyndiotactic polymer from a 1,4-disubstituted butadiene by alternate molecular stacking in the crystalline state . J. Am. Chem. Soc. , 2002 , 124 ( 33 ), 9676 – 9677 .

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 .

Samanta, R. ; Kitagawa, D. ; Mondal, A. ; Bhattacharya, M. ; Annadhasan, M. ; Mondal, S. ; Chandrasekar, R. ; Kobatake, S. ; Reddy, C. M . Mechanical actuation and patterning of rewritable crystalline monomer-polymer heterostructures via topochemical polymerization in a dual-responsive photochromic organic material . ACS Appl. Mater. Interfaces , 2020 , 12 ( 14 ), 16856 – 16863 .

Anderson, C. L. ; Li, H. ; Jones, C. G. ; Teat, S. J. ; Settineri, N. S. ; Dailing, E. A. ; Liang, J. T. ; Mao, H. Y. ; Yang, C. Q. ; Klivansky, L. M. ; Li, X. L. ; Reimer, J. A. ; Nelson, H. M. ; Liu, Y . Solution-processable and functionalizable ultra-high molecular weight polymers via topochemical synthesis . Nat. Commun. , 2021 , 12 ( 1 ), 6818 .

Itoh, T. ; Nomura, S. ; Nakasho, H. ; Uno, T. ; Kubo, M. ; Tohnai, N. ; Miyata, M . Halogen bond effect for single-crystal-to-single-crystal transformation: topochemical polymerization of substituted quinodimethane . Macromolecules , 2015 , 48 ( 15 ), 5450 – 5455 .

Sun, A. W. ; Lauher, J. W. ; Goroff, N. S . Preparation of poly(diiododiacetylene), an ordered conjugated polymer of carbon and iodine . Science , 2006 , 312 ( 5776 ), 1030 – 1034 .

Kane, J. J. ; Liao, R. F. ; Lauher, J. W. ; Fowler, F. W . Preparation of layered diacetylenes as a demonstration of strategies for supramolecular synthesis . J. Am. Chem. Soc. , 1995 , 117 ( 48 ), 12003 – 12004 .

Hsu, T. J. ; Fowler, F. W. ; Lauher, J. W . Preparation and structure of a tubular addition polymer: a true synthetic nanotube . J. Am. Chem. Soc. , 2012 , 134 ( 1 ), 142 – 145 .

Baughman, R. H . Solid-state synthesis of large polymer single crystals . J. Polym. Sci. Polym. Phys. Ed. , 1974 , 12 ( 8 ), 1511 – 1535 .

Baillargeon, P. ; Robidas, R. ; Legault, C. Y. ; Rahem, T. ; Paré Fouapon, A. ; Boivin, S. M . Rapid access to polychlorodiacetylene single crystals through H-bond templating and computations on helical PDA oligomers . Cryst. Growth Des. , 2020 , 20 ( 9 ), 5648 – 5656 .

Xiao, J. ; Yang, M. ; Lauher, J. ; Fowler, F . A supramolecular solution to a long-standing problem: the 1,6-polymerization of a triacetylene . Angew. Chem. , 2000 , 112 ( 12 ), 2216 – 2219 .

Pathigoolla, A. ; Sureshan, K. M . A crystal-to-crystal synthesis of triazolyl-linked polysaccharide . Angew. Chem. Int. Ed. , 2013 , 52 ( 33 ), 8671 – 8675 .

Athiyarath, V. ; Madhusudhanan, M. C. ; Kunnikuruvan, S. ; Sureshan, K. M . Secondary structure tuning of a pseudoprotein between β -meander and α -helical forms in the solid-state . Angew. Chem. Int. Ed. , 2022 , 61 ( 4 ), e202280462 .

Mohanrao, R. ; Sureshan, K. M . Synthesis and reversible hydration of a pseudoprotein, a fully organic polymeric desiccant by multiple single-crystal-to-single-crystal transformations . Angew. Chem. , 2018 , 130 ( 38 ), 12615 – 12619 .

Athiyarath, V. ; Sureshan, K. M . Designed synthesis of a 1D polymer in twist-stacked topology via single-crystal-to-single-crystal polymerization . Angew. Chem. , 2020 , 132 ( 36 ), 15710 – 15715 .

Athiyarath, V. ; Sureshan, K. M . Spontaneous single-crystal-to-single-crystal evolution of two cross-laminated polymers . Angew. Chem. , 2019 , 131 ( 2 ), 622 – 627 .

Hasegawa, M. ; Suzuki, Y. ; Suzuki, F. ; Nakanishi, H . Four-center type photopolymerization in the solid state. I. Polymerization of 2,5-distyrylpyrazine and related compounds . J. Polym. Sci. A-1 Polym. Chem. , 1969 , 7 ( 2 ), 743 – 752 .

Wang, Z. H. ; Miller, B. ; Butz, J. ; Randazzo, K. ; Wang, Z. D. ; Chu, Q. R . Polyladderane constructed from a gemini monomer through photoreaction . Angew. Chem. Int. Ed. , 2017 , 56 ( 40 ), 12155 – 12159 .

Guo, Q. H. ; Jia, M. P. ; Liu, Z. C. ; Qiu, Y. Y. ; Chen, H. L. ; Shen, D. K. ; Zhang, X. ; Tu, Q. ; Ryder, M. R. ; Chen, H. Y . Single-crystal polycationic polymers obtained by single-crystal-to-single-crystal photopolymerization . J. Am. Chem. Soc. , 2020 , 142 ( 13 ), 6180 – 6187 .

Liu, Y. ; Guan, X. R. ; Wang, D. C. ; Stoddart, J. F. ; Guo, Q. H . Soluble and processable single-crystalline cationic polymers . J. Am. Chem. Soc. , 2023 , 145 ( 24 ), 13223 – 13231 .

Wang, H. ; Zhao, Y. J . Single-crystal-to-single-crystal polymerization and photomechanical motion in a metal-free molecular crystal . CCS Chem. , 2026 , 1 – 30 .

Bhandary, S. ; Beliš, M. ; Shukla, R. ; Bourda, L. ; Kaczmarek, A. M. ; Van Hecke, K . Single-crystal-to-single-crystal photosynthesis of supramolecular organoboron polymers with dynamic effects . J. Am. Chem. Soc. , 2024 , 146 ( 12 ), 8659 – 8667 .

Hou, X. D. ; Wang, Z. H. ; Lee, J. ; Wysocki, E. ; Oian, C. ; Schlak, J. ; Chu, Q. R . Synthesis of polymeric ladders by topochemical polymerization . Chem. Commun. , 2014 , 50 ( 10 ), 1218 – 1220 .

Mori, Y. ; Matsumoto, A . Molecular stacking and photoreactions of fluorine-substituted benzyl muconates in the crystals . Cryst. Growth Des. , 2007 , 7 ( 2 ), 377 – 385 .

Hoang, T. ; Lauher, J. W. ; Fowler, F. W . The topochemical 1,6-polymerization of a triene . J. Am. Chem. Soc. , 2002 , 124 ( 36 ), 10656 – 10657 .

Itoh, T. ; Suzuki, T. ; Uno, T. ; Kubo, M. ; Tohnai, N. ; Miyata, M . Cis -specific topochemical polymerization: alternating copolymerization of 7,7,8,8-tetrakis(methoxycarbonyl)quinodimethane with 7,7,8,8-tetracyanoquinodimethane in the solid state . Angew. Chem. Int. Ed. , 2011 , 50 ( 10 ), 2253 – 2256 .

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 . Z. Naturforsch., B: J. Chem. Sci. , 1969 , 24 ( 7 ), 824 – 832 .

Dory, Y. L. ; Caron, M. ; Duguay, V. O. ; Chicoine-Ouellet, L. ; Fortin, D. ; Baillargeon, P . Preparation and single crystal structure determination of the first biobased furan-polydiacetylene using topochemical polymerization . Crystals , 2019 , 9 ( 9 ), 448 .

Tabata, H. ; Kuwamoto, K. ; Okuno, T . Conformational polymorphs and solid-state polymerization of 9-(1,3-butadiynyl)carbazole derivatives . J. Mol. Struct. , 2016 , 1106 , 452 – 459 .

Goroff, N. S. ; Curtis, S. M. ; Webb, J. A. ; Fowler, F. W. ; Lauher, J. W . Designed cocrystals based on the pyridine-iodoalkyne halogen bond . Org. Lett. , 2005 , 7 ( 10 ), 1891 – 1893 .

Jordan, R. S. ; Wang, Y. ; McCurdy, R. D. ; Yeung, M. T. ; Marsh, K. L. ; Khan, S. I. ; Kaner, R. B. ; Rubin, Y . Synthesis of graphene nanoribbons via the topochemical polymerization and subsequent aromatization of a diacetylene precursor . Chem , 2016 , 1 ( 1 ), 78 – 90 .

Baughman, R. H . Solid-state polymerization of diacetylenes . J. Appl. Phys. , 1972 , 43 ( 11 ), 4362 – 4370 .

Pathan, J. R. ; Balan, H. ; Das, K. ; Reddy, C. M. ; Sureshan, K. M . Single-crystal-to-single-crystal synthesis of a polymer in two distinct topologies . Angew. Chem. Int. Ed. , 2025 , 64 ( 15 ), e202500646 .

Zhu, Z. B. ; Li, X. M. ; Liu, L. ; Xu, Y. K. ; Qu, D. H. ; Tian, H. ; Zhang, Q . Single-crystalline poly(disulfide)s enabled by phototriggered topochemical ring-opening polymerization of 1,2-dithiolane . J. Am. Chem. Soc , 2025 , 147 ( 46 ), 42743 – 42751 .

Views

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

Practice of Seminar-based Teaching for “Polymer Structure and Properties” in the Excellent Engineer Program

Structural Characterization and Performance of Functionalized Carbon Nanotube Reinforced Tetrapropylene Fluororubber Composites

Shape Memory Properties of Trans-polyisoprene/Polybutene-1 Dynamic Vulcanization System

Influence of Phosphorus-containing Polyol OP550 on the Thermal, Mechanical, and Flame-retardant Performance of Poly(tetramethylene ether glycol)-based Thermoplastic Polyurethane

Efficient Chemical Degradation of Styrene‐butadiene Rubber Vulcanizate toLiquid Rubber by a Synergistic Catalytic System of Cp2ZrCl2/LiAlH4

Related Author

WANG Xiu-dong

WANG Hui

ZHAO Ying-jie

LIU Hui

Related Institution

State Key Laboratory of Advanced Optical Polymer and Manufacturing Technology, College of Polymer Science and Engineering, Qingdao University of Science and Technology

⁰