Twelve novel Ag⁺/UO₂²⁺ heterometallic complexes have been prepared and characterized via structural, spectroscopic, and computational methods to probe the effects of Ag–oxo interactions on bonding and photophysical properties of the uranyl cation. Structural characterization reveals Ag–oxo interaction distances ranging from 2.475(3) Å to 4.287(4) Å. These interactions were probed using luminescence and Raman spectroscopy which displayed little effect on the luminescence intensity and the energy of the Raman active UO symmetric stretch peak as compared to previously reported Pb–oxo interactions. Computational efforts via density functional theory-based natural bond orbital analysis revealed that the highest stabilization energy associated with the Ag–oxo interaction had a value of only 11.03 kcal mol⁻¹ and that all other energy values fell at 7.05 kcal mol⁻¹ or below indicating weaker interactions relative to those previously reported for Pb²⁺/UO₂²⁺ heterometallic compounds. In contrast, quantum theory of atoms in molecules analysis of bond critical point electron density values indicated higher electron density in Ag–oxo interactions as compared to Pb–oxo interactions which suggests more covalent character with the Ag⁺. Overall, this data indicates that Ag⁺ has a less significant effect on UO₂²⁺ bonding and photophysical properties as compared to other Pb²⁺, likely due to the high polarizability of the cation.

中文翻译：

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Ag+/UO22+ 配合物中 Ag-oxo 相互作用的光谱、结构和计算研究

已经制备了12 种新型 Ag ⁺ /UO ₂ ²⁺异金属配合物，并通过结构、光谱和计算方法对其进行了表征，以探索 Ag-oxo 相互作用对铀酰阳离子的键合和光物理性质的影响。结构表征显示 Ag-oxo 相互作用距离从 2.475(3) Å 到 4.287(4) Å。使用发光和拉曼光谱探测这些相互作用，与先前报道的 Pb-氧代相互作用相比，这些相互作用对拉曼活性 U O 对称伸缩峰的发光强度和能量几乎没有影响。计算工作通过基于密度泛函理论的自然键轨道分析表明，与 Ag-oxo 相互作用相关的最高稳定能量值仅为 11.03 kcal mol ^-1，而所有其他能量值均降至 7.05 kcal mol ^-1或更低，表明相互作用较弱相对于先前报道的 Pb ²⁺ /UO ₂ ²⁺异金属化合物。相比之下，分子中原子的量子理论对键临界点电子密度值的分析表明，与 Pb-oxo 相互作用相比，Ag-oxo 相互作用中的电子密度更高，这表明 Ag ⁺具有更多的共价特性。总体而言，该数据表明 Ag ^{+与其他Pb 2+}相比，对UO ₂ ²⁺键合和光物理性质的影响较小，这可能是由于阳离子的高极化率。