Robust π‑Stacking-Derived Metallic Conductivity in Tetrathiafulvalene-Based Coordination Polymers

Tetrathiafulvalene (TTF)-based conducting coordination polymers (CCPs) are distinguished by their extended π-conjugation and rich redox chemistry, which can enable metallic conductivity comparable to or exceeding that of traditional inorganic semiconductors. However, the mechanisms underlying their conductivity and magnetic behavior remain poorly understood due to the complex interplay of π-conjugation, metal–ligand interactions, dimensionality, and structural disorder. Here, we employ density functional theory to investigate NiTTFtt and related metal-TTFtt systems (Pd, Pt, Sn, Co, Cu, and Fe). Our findings establish metallic conduction in TTFtt-based CCPs as an intrinsic property of the π-conjugated backbone, largely independent of metal identity and structural disorder. This intrinsic robustness, combined with tunable magnetic features and mechanical flexibility, highlights the potential of TTFtt-based CCPs as multifunctional molecular conductors for reliable performance in next-generation electronic materials.