Wang Miaomiao, He Zhixin, Chen Meng, Wang Yanlan
Department of Chemistry and Chemical Engineering, Liaocheng University 252059 Liaocheng China
RSC Adv. 2023 Oct 10;13(42):29689-29694. doi: 10.1039/d3ra04460b. eCollection 2023 Oct 4.
A series of sulfonate anions paired aromatic triangular palladium clusters 3-7, abbreviated as [Pd][ArSO], were synthesized using a simple "one pot" method, and gave excellent isolated yields (90-95%). Their structures and properties have been fully characterized and further investigated by fluorescence, single crystal X-ray Diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS). In varying organic solvents, they presented apparently stronger absorption and emission in MeOH, driven by the combined interactions of hydrogen bonds and polarity. The crystallographic data demonstrated that the methyl orange ion stabilized complex 7 possessed a symmetric metallic core which was still coplanar and almost equilateral, jointly influenced by the giant hindrance and milder donating effect from the sulfonate. The binding energies for Pd 3d and Pd 3d measured by XPS presented at 336.55 and 342.00 eV, respectively. These data were much lower than that of a usual Pd 3d and significantly higher than that of a Pd species, further proving the unified palladium valence state (+4/3) in the tri-palladium core and its aromaticity featured by the cyclic electron delocalization.
通过简单的“一锅法”合成了一系列磺酸根阴离子配对的芳香族三角形钯簇3-7，简称为[Pd][ArSO]，分离产率优异（90-95%）。通过荧光、单晶X射线衍射（XRD）和X射线光电子能谱（XPS）对其结构和性质进行了全面表征和进一步研究。在不同的有机溶剂中，由于氢键和极性的共同作用，它们在甲醇中表现出明显更强的吸收和发射。晶体学数据表明，甲基橙离子稳定的配合物7具有对称的金属核心，该核心仍共面且几乎等边，受到磺酸根巨大位阻和较弱给电子效应的共同影响。通过XPS测量的Pd 3d和Pd 3d的结合能分别为336.55和342.00 eV。这些数据远低于通常的Pd 3d，且显著高于Pd物种的数据，进一步证明了三钯核心中统一的钯价态（+4/3）及其以环状电子离域为特征的芳香性。
