Wang Zhiyong, Un Hio-Ieng, Liu Tsai-Jung, Liang Baokun, Polozij Miroslav, Hambsch Mike, Pöhls Jonas F, Weitz R Thomas, Mannsfeld Stefan C B, Kaiser Ute, Heine Thomas, Sirringhaus Henning, Feng Xinliang, Dong Renhao
Max Planck Institute of Microstructure Physics, Weinberg 2, 06120, Halle (Saale), Germany.
Center for Advancing Electronics Dresden (cfaed), Faculty of Chemistry and Food Chemistry, Dresden University of Technology, 01062, Dresden, Germany.
Angew Chem Int Ed Engl. 2025 Mar 24;64(13):e202423341. doi: 10.1002/anie.202423341. Epub 2025 Jan 21.
Electrically conductive coordination polymers (ECCPs), particularly those incorporating benzenehexathiol (BHT) ligands, are emerging as a distinctive class of electronic materials with tunable semiconducting and metallic properties. However, the exploration of novel ECCPs with low-symmetry structures and electrical anisotropy remains under development. Here, we report the on-water surface synthesis of a novel ECCP, namely CuBHT, which exhibits a low-symmetry structure and unique in-plane electrical anisotropy that differs from the well-known CuBHT phase. Utilizing imaging and diffraction techniques, we elucidate the unit cell and crystal structure of CuBHT, revealing an asymmetric arrangement of the kagome resembling lattice connected by two different secondary building units: square planar CuS and non-planar CuS. Theoretical studies indicate that CuBHT is metallic and exhibits in-plane electrical anisotropy due to the structure arranged in interconnected well-conducting CuS chains and less-conducting CuS slabs oriented along single crystal direction. Single-crystal electrical measurements confirm a metallic character characterized by the increase of conductance upon cooling. Notably, the measured conductance along different crystal directions within the ab plane unambiguously reveals a significant anisotropy, with an anisotropic factor reaching ~8. This work demonstrates a novel low-symmetry ECCP and highlights its potential for achieving in-plane electrical anisotropy.
导电配位聚合物（ECCP），特别是那些包含苯六硫醇（BHT）配体的聚合物，正作为一类具有可调半导体和金属特性的独特电子材料而兴起。然而，具有低对称结构和电各向异性的新型ECCP的探索仍在发展中。在此，我们报告了一种新型ECCP即CuBHT在水表面的合成，它具有低对称结构和独特的面内电各向异性，这与著名的CuBHT相不同。利用成像和衍射技术，我们阐明了CuBHT的晶胞和晶体结构，揭示了由两种不同的二级结构单元连接的类似晶格的kagome的不对称排列：平面正方形CuS和非平面CuS。理论研究表明，CuBHT是金属性的，并且由于其结构沿单晶方向排列成相互连接的良好导电的CuS链和导电性较差的CuS平板，从而表现出面内电各向异性。单晶电学测量证实了其金属特性，其特征是随着温度降低电导率增加。值得注意的是，在ab平面内沿不同晶体方向测量的电导率明确显示出显著的各向异性，各向异性因子达到约8。这项工作展示了一种新型的低对称ECCP，并突出了其实现面内电各向异性的潜力。
