Jana Arijit, Wang Yaofeng, Guggolz Lukas, Chen Yaorong, Ganslmaier Franziska, Weinert Bastian, Ruben Mario, Dehnen Stefanie
Institute of Nanotechnology, Karlsruhe Institute of Technology (INT), Kaiserstraße 12, 76131, Karlsruhe, Germany.
Institute of Quantum Materials and Technologies (IQMT), Karlsruhe Institute of Technology, Kaiserstraße 12, 76131, Karlsruhe, Germany.
Small. 2025 Sep;21(38):e06920. doi: 10.1002/smll.202506920. Epub 2025 Aug 8.
Atomically-precise heterometallic nickel-based clusters are an emerging class of functional nanomaterials with intriguing optical and magnetic properties. However, synthetic challenges restrict their exploration in comparison to heterometallic coinage metal-based nanoclusters. This study presents a single-step synthesis of the two new thiolate-bridged copper-nickel cluster compounds [CuNiS(MCP)] (1) and [CuNi(MCP)I] (2) (MCPH = 2-mercaptopyridine; MCP = deprotonated 2-mercaptopyridine) at an elevated temperature. Single-crystal X-ray diffraction reveals that 1 is composed of polymeric strands of linked cluster units. Each of the units exhibit a bicapped trigonal prismatic {CuNi} core that is surrounded by three capping sulfide and six MCP ligands. Cluster 2 features individual clusters, each bearing a hexagonal bipyramidal {CuNi} core with twelve MCP units as well as two iodide ions as additional ligands. In spite of the different aggregation modes, both of these clusters exhibit molecule-like characteristic multiband optical absorption features. Temperature-dependent magnetic susceptibility measurements for 1 revealed dual antiferromagnetic and ferromagnetic coupling among six Ni(II) centers with an S = 2 ground state, while 2 exhibits strong ferromagnetic coupling, whereby the susceptibility increases with decreasing temperature to an S = 4 ground state. This study is an example of solvothermal synthesis of related ligand-supported copper-nickel cluster compounds with structure-specific optical and magnetic properties.
原子精确的异金属镍基簇合物是一类新兴的功能纳米材料，具有引人入胜的光学和磁性。然而，与异金属货币金属基纳米簇相比，合成挑战限制了它们的探索。本研究展示了在高温下一步合成两种新的硫醇盐桥联铜镍簇合物[CuNiS(MCP)] (1)和[CuNi(MCP)I] (2)（MCPH = 2-巯基吡啶；MCP = 去质子化的2-巯基吡啶）。单晶X射线衍射表明，1由连接的簇单元的聚合物链组成。每个单元都呈现出一个双帽三角棱柱形的{CuNi}核，被三个帽状硫化物和六个MCP配体包围。簇合物2具有单个簇，每个簇都带有一个六角双锥{CuNi}核，有十二个MCP单元以及两个碘离子作为额外的配体。尽管聚集模式不同，但这两种簇合物都表现出类似分子的特征多带光学吸收特性。对1进行的温度依赖性磁化率测量揭示了六个Ni(II)中心之间的双重反铁磁和铁磁耦合，基态为S = 2，而2表现出强铁磁耦合，磁化率随温度降低增加至S = 4基态。本研究是溶剂热合成具有结构特异性光学和磁性的相关配体支撑铜镍簇合物的一个实例。
