4.8 Article

Molecular Insertion: A Master Key to Unlock Smart Photoelectric Responses of Covalent Organic Frameworks

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SMALL
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WILEY-V C H VERLAG GMBH
DOI: 10.1002/smll.202302254

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covalent organic frameworks; molecular insertion; non-covalent interactions; photocatalytic reduction; photoelectric responses

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A creative lock-key model based on molecular insertion strategy was used to construct molecular-inserted covalent organic frameworks, allowing for the smart modulation of photoelectric responses. This approach avoids the arduous selection and synthesis conditions required by conventional COFs, providing a promising direction for the construction of late-model photoelectric responsive materials.
Covalent organic frameworks (COFs) show potentials in prominent photoelectric responses by judicious structural design. However, from the selections of monomers and condensation reactions to the synthesis procedures, the acquisition of photoelectric COFs has to meet overmuch high conditions, limiting the breakthrough and modulation in photoelectric responses. Herein, the study reports a creative lock-key model based on molecular insertion strategy. A COF with suitable cavity size, TP-TBDA, is used as the host to load guests. Merely through the volatilization of mixed solution, TP-TBDA and guests can be spontaneously assembled via non-covalent interactions (NCIs) to produce molecular-inserted COFs (MI-COFs). The NCIs between TP-TBDA and guests acted as a bridge to facilitate charge transfer in MI-COFs, unlocking the photoelectric responses of TP-TBDA. By exploiting the controllability of NCIs, the MI-COFs can realize the smart modulation of photoelectric responses by simply changing the guest molecule, thus avoiding the arduous selection of monomers and condensation reactions required by conventional COFs. The construction of molecular-inserted COFs circumvents complicated procedures for achieving performance improvement and modulation, providing a promising direction to construct late-model photoelectric responsive materials.

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