TY - JOUR A1 - Yang, Jin A1 - Ghosh, Samrat A1 - Roeser, Jérôme A1 - Acharjya, Amitava A1 - Penschke, Christopher A1 - Tsutsui, Yusuke A1 - Rabeah, Jabor A1 - Wang, Tianyi A1 - Tameu, Simon Yves Djoko A1 - Ye, Meng-Yang A1 - Grüneberg, Julia A1 - Li, Shuang A1 - Li, Changxia A1 - Schomaecker, Reinhard A1 - Van de Krol, Roel A1 - Seki, Shu A1 - Saalfrank, Peter A1 - Thomas, Arne T1 - Constitutional isomerism of the linkages in donor–acceptor covalent organic frameworks and its impact on photocatalysis JF - Nature Communications N2 - When new covalent organic frameworks (COFs) are designed, the main efforts are typically focused on selecting specific building blocks with certain geometries and properties to control the structure and function of the final COFs. The nature of the linkage (imine, boroxine, vinyl, etc.) between these building blocks naturally also defines their properties. However, besides the linkage type, the orientation, i.e., the constitutional isomerism of these linkages, has rarely been considered so far as an essential aspect. In this work, three pairs of constitutionally isomeric imine-linked donor-acceptor (D-A) COFs are synthesized, which are different in the orientation of the imine bonds (D-C=N-A (DCNA) and D-N=C-A (DNCA)). The constitutional isomers show substantial differences in their photophysical properties and consequently in their photocatalytic performance. Indeed, all DCNA COFs show enhanced photocatalytic H2 evolution performance than the corresponding DNCA COFs. Besides the imine COFs shown here, it can be concluded that the proposed concept of constitutional isomerism of linkages in COFs is quite universal and should be considered when designing and tuning the properties of COFs. Y1 - 2022 U6 - https://doi.org/10.1038/s41467-022-33875-9 SN - 2041-1723 VL - 13 IS - 1 PB - Nature Publishing Group UK CY - [London] ER -