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Controlling the structural parameters in coassembly is crucial for the fabrication of multicomponent functional materials. Here a proof‐of‐concept study is presented to reveal the α‐substituent effect of aromatic amino acids on their selective coassembly with bipyridine binders. With the assistance of X‐ray scattering technique, it is found that individual packing in the solid state as well as bulky effect brought by α‐substitution determines the occurrence of coassembly. A well‐performed hydrogels based on the complexation between certain aromatic amino acids and bipyridine units are successfully constructed, providing unprecedented smart materials with light irradiation‐triggered luminescence. Such hydrogels without the phase separation and photobleaching during light irradiation are able to behave fluorescent imprint materials. This study provides a suitable protocol in rationally designing amino acid residues of short peptides for fabricating self‐assembled multicomponent materials. In addition, this protocol is useful in screening potential functional materials on account of diverse self‐assembly behavior.  相似文献   

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