Single-Atom Tuning of Structural and Optoelectronic Properties in Halogenated Anthracene-Based Covalent Organic Frameworks

Abstract: 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.