@article{YangGhoshRoeseretal.2022, author = {Yang, Jin and Ghosh, Samrat and Roeser, J{\´e}r{\^o}me and Acharjya, Amitava and Penschke, Christopher and Tsutsui, Yusuke and Rabeah, Jabor and Wang, Tianyi and Tameu, Simon Yves Djoko and Ye, Meng-Yang and Gr{\"u}neberg, Julia and Li, Shuang and Li, Changxia and Schomaecker, Reinhard and Van de Krol, Roel and Seki, Shu and Saalfrank, Peter and Thomas, Arne}, title = {Constitutional isomerism of the linkages in donor-acceptor covalent organic frameworks and its impact on photocatalysis}, series = {Nature Communications}, volume = {13}, journal = {Nature Communications}, number = {1}, publisher = {Nature Publishing Group UK}, address = {[London]}, issn = {2041-1723}, doi = {10.1038/s41467-022-33875-9}, pages = {10}, year = {2022}, abstract = {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.}, language = {en} }