A Redox‐Active Tetrathiafulvalene‐Based 3D Covalent Organic Framework with scu Topology for Controllable Charge Transport

Unlike 2D frameworks where conductivity is largely confined to in‐plane transport, the scu topology offers 3D conduction pathways that enhance bulk charge mobility. When integrated with redox‐active species like tetrathiafulvalene (TTF), the scu architecture promotes electron transfer across the 3D network, enabling tunable conductivity. This article presents the construction of a 3‐periodic (4,8)‐c covalent organic framework (COF), TU‐48, adopting a twofold interpenetrated scu net, achieved through the integration of a tetratopic D 2h ‐symmetric rectangular TTF structural motif and an octatopic D 2h ‐symmetric quadrangular prism linker. TU‐48 exhibits high structural order, well‐defined porosity, and redox‐responsive electrochemical behavior. The high‐connectivity 3D COF configuration ensures effective access to TTF redox centers, enabling controlled iodine oxidation and resulting in electrical conductivities of 4.3 × 10 −6 S cm −1 at 298 K and 1.8 × 10 −4 S cm −1 at 393 K. By demonstrating how enhanced structural connectivity in TTF‐bridged 3D covalent lattices enables improved charge‐transport properties, this research fuels innovation in sustainable energy storage solutions and electronics.