Liu Zheng, Fang Jun-Jie, Wang Zhi-Yi, Xie Yun-Peng, Lu Xing
State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, China.
School of Chemistry and Chemical Engineering, Hainan University, No. 58, Renmin Avenue, Haikou 570228, China.
Inorg Chem. 2024 Jun 17;63(24):11146-11154. doi: 10.1021/acs.inorgchem.4c00822. Epub 2024 Jun 5.
Surface ligands play crucial roles in modifying the properties of metal nanoclusters and stabilizing atomically precise structures, and also serve as vital linkers for constructing cluster-based coordination polymers. In this study, we present the results of the solvothermal synthesis of eight novel copper alkynyl clusters incorporating pyridine ligands using a one-pot method. The resulting compounds underwent characterization through elemental analysis, Fourier transform infrared (FT-IR) spectroscopy, powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction (SCXRD). Our observations revealed that distinct pyridine ligands with varying lengths and coordination sites exert significant influence on the structure and dimensionality of the clusters. The structural diversity of these clusters led to the formation of one-dimensional (1D), two-dimensional (2D), or dimer arrangements linked by seven pyridine bridging ligands. Remarkably, these complexes exhibited unique UV-vis absorption and photoluminescence properties, which were influenced by the specific bridging ligand and structural framework. Furthermore, density functional theory (DFT) calculations demonstrated the capability of the conjugated system in the pyridine ligand to impact the band gap of clusters. This study not only unveils the inherent structural diversity in coordination polymers based on copper alkynyl clusters but also offers valuable insights into harnessing ligand engineering for structural and property modulation.
表面配体在修饰金属纳米团簇的性质和稳定原子精确结构方面起着关键作用，并且还作为构建基于团簇的配位聚合物的重要连接体。在本研究中，我们展示了使用一锅法溶剂热合成八种包含吡啶配体的新型铜炔基团簇的结果。所得化合物通过元素分析、傅里叶变换红外（FT-IR）光谱、粉末X射线衍射（PXRD）和单晶X射线衍射（SCXRD）进行表征。我们的观察结果表明，具有不同长度和配位位点的不同吡啶配体对团簇的结构和维度有显著影响。这些团簇的结构多样性导致通过七个吡啶桥连配体形成一维（1D）、二维（2D）或二聚体排列。值得注意的是，这些配合物表现出独特的紫外可见吸收和光致发光性质，这受到特定桥连配体和结构框架的影响。此外，密度泛函理论（DFT）计算表明吡啶配体中的共轭体系能够影响团簇的带隙。本研究不仅揭示了基于铜炔基团簇的配位聚合物中固有的结构多样性，还为利用配体工程进行结构和性能调控提供了有价值的见解。
