Jiang Ningxin, Velliyarat Saranya, Lien Chen-Yu, Nguyen Ha L, Hofmann Jan, Chen Jie-Hao, Ramanathan Arun, Filatov Alexander S, La Pierre Henry S, Patel Shrayesh, Chapman Karena W, Boyn Jan-Niklas, Anderson John S
Department of Chemistry, University of Chicago Chicago Illinois 60637 USA
Department of Chemistry, University of Minnesota Minneapolis Minnesota 55455 USA.
Chem Sci. 2025 Sep 11. doi: 10.1039/d5sc03070f.
Conductive coordination polymers (CPs) with sulfur-based ligands offer strong metal-ligand interactions and redox tunability, making them promising candidates for electronic applications. Tetrathiafulvalene-2,3,6,7-tetrathiolate (TTFtt) is a particularly attractive ligand. However, its strong metal-ligand covalency leads to rapid irreversible metal coordination, limiting control over structure and morphology. Here, we demonstrate structural control in Cu TTFtt CPs using a pre-synthetic redox control strategy. Two new copper-based CPs, CuTTFtt and CuTTFtt, have been synthesized and thoroughly characterized from differentially oxidized TTFtt synthons. CuTTFtt forms a 1D chain, while CuTTFtt adopts a 2D ribbon-like structure. Detailed spectroscopic studies confirm the structures of these materials as well as their ligand and metal oxidation states. Physical property measurements reveal that CuTTFtt exhibits higher conductivity than CuTTFtt. Furthermore, CuTTFtt also shows unusual diamagnetism which contrasts the paramagnetism observed in CuTTFtt and the related material NiTTFtt. Density functional theory (DFT) further elucidates the physical properties of these CPs and supports the observed conductivity trends. This study expands the structural landscape of TTFtt-based CPs and further establishes how redox-doping can tune CP structure and physical properties.
具有硫基配体的导电配位聚合物（CPs）提供了强大的金属-配体相互作用和氧化还原可调性，使其成为电子应用中有前景的候选材料。四硫富瓦烯-2,3,6,7-四硫醇盐（TTFtt）是一种特别有吸引力的配体。然而，其强大的金属-配体共价性导致快速不可逆的金属配位，限制了对结构和形态的控制。在这里，我们展示了使用合成前氧化还原控制策略对铜TTFtt CPs进行结构控制。通过差异氧化的TTFtt合成子合成并全面表征了两种新的铜基CPs，即CuTTFtt和CuTTFtt。CuTTFtt形成一维链，而CuTTFtt采用二维带状结构。详细的光谱研究证实了这些材料的结构以及它们的配体和金属氧化态。物理性质测量表明，CuTTFtt的导电性高于CuTTFtt。此外，CuTTFtt还表现出不寻常的抗磁性，这与在CuTTFtt和相关材料NiTTFtt中观察到的顺磁性形成对比。密度泛函理论（DFT）进一步阐明了这些CPs的物理性质，并支持了观察到的电导率趋势。这项研究扩展了基于TTFtt的CPs的结构范围，并进一步确定了氧化还原掺杂如何调节CP的结构和物理性质。
