Dynamic Interchain Motion in 1D Tetrathiafulvalene‐Based Coordination Polymers for Highly Sensitive Molecular Recognition

Abstract The application of electrically conductive 1D coordination polymers (1D CPs) in nanoelectronic molecular recognition is theoretically promising yet rarely explored due to the challenges in their synthesis and optimization of electrical properties. In this regard, two tetrathiafulvalene‐based 1D CPs, namely [Co( m ‐H ₂ TTFTB)(DMF) ₂ (H ₂ O)] _n (Co‐ m ‐TTFTB), and {[Ni( m ‐H ₂ TTFTB)(CH ₃ CH ₂ OH) _1.5 (H ₂ O) _1.5 ]·(H ₂ O) _0.5 } _n (Ni‐ m ‐TTFTB) are successfully constructed. The shorter S···S contacts between the [M(solvent) ₃ ( m ‐H ₂ TTFTB)] _n chains contribute to a significant improvement in their electrical conductivities. The powder X‐ray diffraction (PXRD) under different organic solvents reveals the flexible and dynamic structural characteristic of M‐ m ‐TTFTB, which, combined with the 1D morphology, lead to their excellent performance for sensitive detection of volatile organic compounds. Co‐ m ‐TTFTB achieves a limit of detection for ethanol vapor down to 0.5 ppm, which is superior to the state‐of‐the‐art chemiresistive sensors based on metal‐organic frameworks or organic polymers at room temperature. In situ diffuse reflectance infrared Fourier transform spectroscopy, PXRD measurements and density functional theory calculations reveal the molecular insertion sensing mechanism and the corresponding structure–function relationship. This work expands the applicable scenario of 1D CPs and opens a new realm of 1D CP‐based nanoelectronic sensors for highly sensitive room temperature gas detection.