Electrosynthesis of a Metal–Organic Framework Single Crystal with Narrow Bandgap

The rational synthesis of metal–organic frameworks (MOFs) plays a critical role in studying the correlation between their structure and properties. Among various synthesis strategies, electrosynthesis has emerged as a promising approach for the rapid and controllable preparation of various MOFs. Herein, a novel MOF single crystal featuring the porphyrin block and the coordinated linkage between pyridine and cadmium (Cd 2+ ) ions is electrolytically synthesized as millimeter‐sized single crystal under mild ambient condition. Temperature‐dependent changes in its 3D cross‐interpenetrating topology are systematically investigated. Moreover, the as‐synthesized MOF single crystal exhibits typical semiconductive behavior with a narrow bandgap of 1.12 eV. This study exploits the potential of electrosynthesis as a clean and scalable approach to address the synthesis of MOF single crystal.