Managing Lattice Strain Enables Irreversible Single‐Crystal‐to‐Single‐Crystal Transformation of Covalent Organic Frameworks
Abstract
ABSTRACT Covalent organic frameworks (COFs) typically rely on reversible covalent chemistry to achieve crystallinity, whereas irreversible and rigid linkages are generally required to achieve enhanced robustness and extended π‐conjugation. Single‐crystal‐to‐single‐crystal (SCSC) transformation offers a promising route to access such frameworks; however, irreversible bond reconfiguration imposes permanent mechanical strain that often disrupts lattice order. Here, we demonstrate sulfur‐assisted SCSC transformation of imine‐linked COFs into rigid benzothiazole‐linked frameworks with experimentally resolved atomic structures. Time‐resolved structural analyses uncover two distinct stress‐accommodation pathways‐cooperative lattice adaptation and stress‐driven transient domain reconstruction that enable irreversible bond fusion while preserving long‐range crystallographic order. The resulting single‐crystalline thiazole‐linked COFs exhibit enhanced chemical stability, rigidified pore architectures, and improved optoelectronic performance. This study establishes a mechanistic framework for managing lattice strain during irreversible covalent transformation and provides a general design principle for constructing structurally robust crystalline polymers.
Article Details
Authors (16)
Lan Xia
Hongfei Ma
Zhilv Wang
Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education GBRCE For Functional Molecular Engineering Guangdong Engineering Technology Research Centre For High‐performance Organic and Polymer Photoelectric Functional Films School of Chemistry IGCME and State Key Laboratory of Optoelectronic Materials and Technologies Sun Yat‐sen University Guangzhou China
Yuyao Li
Materdicine Lab, School of Life Sciences
Zeyue Zhang
College of Chemistry and Molecular Engineering
Jian Li
Zhipeng Zhou
Yonghang Yang
Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education GBRCE For Functional Molecular Engineering Guangdong Engineering Technology Research Centre For High‐performance Organic and Polymer Photoelectric Functional Films School of Chemistry IGCME and State Key Laboratory of Optoelectronic Materials and Technologies Sun Yat‐sen University Guangzhou China
Ziyuan Zhang
Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education GBRCE For Functional Molecular Engineering Guangdong Engineering Technology Research Centre For High‐performance Organic and Polymer Photoelectric Functional Films School of Chemistry IGCME and State Key Laboratory of Optoelectronic Materials and Technologies Sun Yat‐sen University Guangzhou China
Yuexian Hong
Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education GBRCE For Functional Molecular Engineering Guangdong Engineering Technology Research Centre For High‐performance Organic and Polymer Photoelectric Functional Films School of Chemistry IGCME and State Key Laboratory of Optoelectronic Materials and Technologies Sun Yat‐sen University Guangzhou China
Rui‐Biao Lin
Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education GBRCE For Functional Molecular Engineering Guangdong Engineering Technology Research Centre For High‐performance Organic and Polymer Photoelectric Functional Films School of Chemistry IGCME and State Key Laboratory of Optoelectronic Materials and Technologies Sun Yat‐sen University Guangzhou China
Jingyun Fang
Institute of Ecology, College of Urban and Environmental Sciences, and State Key Laboratory of Vegetation Structure, Function and Construction, Peking University
Jie‐Peng Zhang
Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education GBRCE For Functional Molecular Engineering Guangdong Engineering Technology Research Centre For High‐performance Organic and Polymer Photoelectric Functional Films School of Chemistry IGCME and State Key Laboratory of Optoelectronic Materials and Technologies Sun Yat‐sen University Guangzhou China
Wei Liu
Junliang Sun
College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences
Zhikun Zheng
Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education GBRCE For Functional Molecular Engineering Guangdong Engineering Technology Research Centre For High‐performance Organic and Polymer Photoelectric Functional Films School of Chemistry IGCME and State Key Laboratory of Optoelectronic Materials and Technologies Sun Yat‐sen University Guangzhou China