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| Main Authors: | , , , , , , , , , |
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| Format: | Preprint |
| Published: |
2026
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| Subjects: | |
| Online Access: | https://arxiv.org/abs/2601.12103 |
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| _version_ | 1866908773253120000 |
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| author | Paliušytė, Klaudija Fuchs, Laura Xu, Zehua Liu, Kuangjie Roztocki, Kornel Sun, Shuo Zipse, Hendrik Hartschuh, Achim Ortmann, Frank Schneider, Jenny |
| author_facet | Paliušytė, Klaudija Fuchs, Laura Xu, Zehua Liu, Kuangjie Roztocki, Kornel Sun, Shuo Zipse, Hendrik Hartschuh, Achim Ortmann, Frank Schneider, Jenny |
| contents | Strategies for tuning structural and (opto-)electronic properties are fundamental to the rational design of functional materials. Here, we present a molecular design approach for precisely modulating the optoelectronic properties of covalent organic frameworks (COFs) through single-atom halogen substitution on $π$-extended anthracene linkers. Using a Wurster-type tetratopic amine (W-NH$_2$) and a series of anthracene-based dialdehydes bearing H, Cl, Br, or I at the 2-position, a family of imine-linked COFs, W-A-X (X = H, Cl, Br, I), was synthesized, all displaying well-ordered porous structures. The halogen substituent strongly influences framework formation, with brominated COFs forming substantially larger crystalline domains than their chloro- and iodo-functionalized analogues. UV-vis absorption and photoluminescence measurements reveal a systematic redshift across the series $(\mathrm{H < Cl < Br < I})$, demonstrating that a single-atom modification effectively tunes the optical response. Time-dependent density functional theory calculations on both isolated fragments and extended COF models attribute these trends to halogen-induced changes in the COF band structure and provide a mechanistic understanding of how single-atom substitution influences the optoelectronic properties of the extended $π$-framework. Overall, this study establishes single-atom halogen substitution as a powerful and modular strategy for tailoring the structural and optical properties of anthracene-based COFs. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2601_12103 |
| institution | arXiv |
| publishDate | 2026 |
| record_format | arxiv |
| spellingShingle | Single-Atom Tuning of Structural and Optoelectronic Properties in Halogenated Anthracene-Based Covalent Organic Frameworks Paliušytė, Klaudija Fuchs, Laura Xu, Zehua Liu, Kuangjie Roztocki, Kornel Sun, Shuo Zipse, Hendrik Hartschuh, Achim Ortmann, Frank Schneider, Jenny Materials Science Strategies for tuning structural and (opto-)electronic properties are fundamental to the rational design of functional materials. Here, we present a molecular design approach for precisely modulating the optoelectronic properties of covalent organic frameworks (COFs) through single-atom halogen substitution on $π$-extended anthracene linkers. Using a Wurster-type tetratopic amine (W-NH$_2$) and a series of anthracene-based dialdehydes bearing H, Cl, Br, or I at the 2-position, a family of imine-linked COFs, W-A-X (X = H, Cl, Br, I), was synthesized, all displaying well-ordered porous structures. The halogen substituent strongly influences framework formation, with brominated COFs forming substantially larger crystalline domains than their chloro- and iodo-functionalized analogues. UV-vis absorption and photoluminescence measurements reveal a systematic redshift across the series $(\mathrm{H < Cl < Br < I})$, demonstrating that a single-atom modification effectively tunes the optical response. Time-dependent density functional theory calculations on both isolated fragments and extended COF models attribute these trends to halogen-induced changes in the COF band structure and provide a mechanistic understanding of how single-atom substitution influences the optoelectronic properties of the extended $π$-framework. Overall, this study establishes single-atom halogen substitution as a powerful and modular strategy for tailoring the structural and optical properties of anthracene-based COFs. |
| title | Single-Atom Tuning of Structural and Optoelectronic Properties in Halogenated Anthracene-Based Covalent Organic Frameworks |
| topic | Materials Science |
| url | https://arxiv.org/abs/2601.12103 |