Self-sorting is commonly observed in complex reaction systems, which has been utilized to guide the formation of single major by-design molecules. However, most studies have been focused on non-covalent systems, and using self-sorting to achieve covalently bonded architectures is still relatively less explored. Herein, we first demonstrated the dynamic nature of spiroborate linkage and systematically studied the selfsorting behavior observed in the transformation between spiroborate-linked well-defined polymeric and molecular architectures, which is enabled by spiroborate bond exchange. The scrambling between a macrocycle and a 1D helical covalent polymer led to the formation of a molecular cage, whose structures are all unambiguously elucidated by single-crystal X-ray diffraction. The results indicate that the molecular cage is the thermodynamically favored product in this multi-component reaction system. This work represents the first example of a 1D polymeric architecture transforming into a shape-persistent molecular cage, driven by dynamic covalent self-sorting. This study will further guide the design of spiroborate-based materials and open the possibilities for the development of novel complex yet responsive dynamic covalent molecular or polymeric systems.
Two covalent organic frameworks consisting of carbazolylene-ethynylene shape-persistent macrocycles with azine (MC-COF-1) or imine (MC-COF-2) linkages were synthesized via imine condensation. The obtained 2D frameworks are fully conjugated which imparts semiconducting properties. In addition, the frameworks showed high porosity with aligned accessible porous channels along the z axis, serving as an ideal platform for post-synthetic incorporation of I 2 into the channels to enable electrical conductivity. The resulting MC-COF-1 showed an electrical conductivity up to 7.8 × 10 À 4 S cm À 1 at room temperature upon I 2 doping with the activation energy as low as 0.09 eV. Furthermore, we demonstrated that the electrical properties of both MC-COFs are switchable between electron-conducting and insulating states by simply implementing doping-regenerating cycles. The knowledge gained in this study opens new possibilities for the future development of tunable conductive 2D organic materials.
Self‐sorting is commonly observed in complex reaction systems, which has been utilized to guide the formation of single major by‐design molecules. However, most studies have been focused on non‐covalent systems, and using self‐sorting to achieve covalently bonded architectures is still relatively less explored. Herein, we first demonstrated the dynamic nature of spiroborate linkage and systematically studied the self‐sorting behavior observed in the transformation between spiroborate‐linked well‐defined polymeric and molecular architectures, which is enabled by spiroborate bond exchange. The scrambling between a macrocycle and a 1D helical covalent polymer led to the formation of a molecular cage, whose structures are all unambiguously elucidated by single‐crystal X‐ray diffraction. The results indicate that the molecular cage is the thermodynamically favored product in this multi‐component reaction system. This work represents the first example of a 1D polymeric architecture transforming into a shape‐persistent molecular cage, driven by dynamic covalent self‐sorting. This study will further guide the design of spiroborate‐based materials and open the possibilities for the development of novel complex yet responsive dynamic covalent molecular or polymeric systems.
Two covalent organic frameworks consisting of carbazolylene-ethynylene shape-persistent macrocycles with azine (MC-COF-1) or imine (MC-COF-2) linkages were synthesized via imine condensation. The obtained 2D frameworks are fully conjugated which imparts semiconducting properties. In addition, the frameworks showed high porosity with aligned accessible porous channels along the z axis, serving as an ideal platform for post-synthetic incorporation of I 2 into the channels to enable electrical conductivity. The resulting MC-COF-1 showed an electrical conductivity up to 7.8 × 10 À 4 S cm À 1 at room temperature upon I 2 doping with the activation energy as low as 0.09 eV. Furthermore, we demonstrated that the electrical properties of both MC-COFs are switchable between electron-conducting and insulating states by simply implementing doping-regenerating cycles. The knowledge gained in this study opens new possibilities for the future development of tunable conductive 2D organic materials.
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