Ningxia Key Laboratory for Photovoltaic Materials, School of Materials and New Energy, Ningxia University, Yinchuan 750021, Ningxia, China.
Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, Tehran 14115175, Iran.
Inorg Chem. 2023 Jul 3;62(26):10185-10192. doi: 10.1021/acs.inorgchem.3c00811. Epub 2023 Jun 20.
The metallophilic properties, spherical configuration, and flexible coordination of silver ions make them prone to create various coordination modes and structural features. Therefore, with the increase of the complexities of self-assembly, the effect of various synthetic conditions in the final structure of silver compounds becomes diverse and attractive. In this study, two new silver polyclusters, 16- and 21-nuclearity, protected by multiple ligands including alkynyl, trifluoroacetate, and diphenylphosphinate, were synthesized and characterized by single-crystal X-ray diffraction, powder X-ray diffraction, and Fourier transform infrared (FTIR) spectroscopy. The optical properties and thermal stability of the polyclusters were studied by solid-state ultraviolet-visible (UV-vis) absorption and solid UV-vis diffuse reflectance spectra and gravimetric analysis, respectively. The formation of the two polyclusters can be fine-controlled by simply adjusting the stoichiometric ratio of diphenylphosphinate ligands to silver precursors under the same synthetic condition, leading to the different coordination modes between ligands and Ag centers. This work shows a facile and template-free method to synthesize and control the silver polycluster assembly, encouraging further development of new polyclusters with the potential for various applications.
银离子的亲金属性质、球形构象和灵活的配位使得它们易于形成各种配位模式和结构特征。因此，随着自组装复杂性的增加，各种合成条件对银化合物最终结构的影响变得多样化和有吸引力。在这项研究中，我们合成并通过单晶 X 射线衍射、粉末 X 射线衍射和傅里叶变换红外（FTIR）光谱对两种新型银多核簇（16 核和 21 核）进行了表征，这些多核簇由炔基、三氟乙酸根和二苯膦酸酯等多种配体保护。通过固态紫外-可见（UV-vis）吸收和固态 UV-vis 漫反射光谱以及重量分析研究了多核簇的光学性质和热稳定性。通过在相同的合成条件下，简单地调整二苯膦酸酯配体与银前体的化学计量比，可以精细控制这两种多核簇的形成，从而导致配体与 Ag 中心之间的不同配位模式。这项工作展示了一种简便且无模板的方法来合成和控制银多核簇的组装，鼓励进一步开发具有各种应用潜力的新型多核簇。
