Porous Hybrid Organic–Metal Chalcogenides with Tubular SBUs and Doping‐Enhanced Conductivity for Electrochemical Energy Storage

Organic‐Metal Chalcogenides (OMCs) are a class of coordination polymers featuring metal chalcogenide subunits linked by conjugated organic units through carbon–chalcogen bonds, whose electrical conducting properties benefit from the continuous metal‐chalcogenides networks. Doping is a well‐established strategy to control electrical properties and tune functionality for conducting materials, however doping studies on OMCs remain relatively rare to date, because most OMCs reported are nonporous. In this work, a porous OMC is successfully synthesized, named Cu‐I‐TMB (TMB = 1,3,5‐tris(4‐mercaptophenyl)benzene) by enlarging the diameter of a tubular secondary building unit (SBU) through encapsulation of hydrogen iodide, and subsequently demonstrate molecular iodine doping of it. The resultant I 2 @Cu‐I‐TMB retains its crystallinity and displays enhanced conductivity by three orders of magnitude. Moreover, its electrochemical energy storage performance as cathode materials of aqueous zinc‐iodine battery reveals a reversible capacity of 236 mAh g −1 at a current density of 50 mA g −1 . This work introduces a novel strategy for designing porous metal‐thiolate based conductive coordination polymers and demonstrates that chemical doping can effectively modulate their structural and functional properties without compromising crystallinity.