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This work proves the existence and chemical addressability of defined edge groups of a 2D polymer. Pseudohexagonally prismatic single crystals consisting of layered stacks of a 2D polymer are used. They should expose anthracene-based edge groups at the six (100) but not at the two pseudohexagonal (001) and (001̅) faces. The crystals are reacted with the isotopically enriched dienophiles maleic anhydride and a C18-alkyl chain-modified maleimide.
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