Effects of Diglyme on Au Nanocluster Formation: Mechanism, 1H NMR, and Bonding,The Journal of Physical Chemistry A

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Effects of Diglyme on Au Nanocluster Formation: Mechanism, 1H NMR, and Bonding
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2022-10-12 , DOI: 10.1021/acs.jpca.2c04218
Yuchen Wang ₁ , Alice Li _{1,

2} , Jacqueline Pinkerton _{1,

3} , Christine M Aikens ₁

Affiliation

Recently, diglyme was applied as a solvent in the synthesis of a luminescent gold–thiolate nanocluster. However, the interactions between the diglyme and the gold nanocluster and the intrinsic mechanism of the diglyme-assisted nanocluster growth have not been examined. In this work, we use density functional theory (DFT) to propose a plausible pathway for diglyme-assisted Au(I)–thiolate synthesis; the reaction energies are found to be negative in every step. ¹H NMR calculations are applied to characterize how the environment arising from different gold motifs affects the chemical shifts of the protons on diglyme, which experience strong downfield shifts. Extended transition state-natural orbitals for chemical valence (ETS-NOCV) theory is also utilized to examine the interactions between diglyme and gold clusters as well as a Au₂₀(SR)₁₅ nanocluster. Our work demonstrates that diglyme can play an important role in the synthetic mechanism yielding gold nanoclusters and provides insights into the diglyme–nanocluster binding motifs and resulting NMR chemical shifts.

中文翻译：

Diglyme 对 Au 纳米团簇形成的影响：机理、1H NMR 和键合

最近，二甘醇二甲醚被用作合成发光硫醇金纳米簇的溶剂。然而，二甘醇二甲醚与金纳米团簇之间的相互作用以及二甘醇二甲醚辅助纳米团簇生长的内在机制尚未得到研究。在这项工作中，我们使用密度泛函理论 (DFT) 提出了一种可行的二甘醇二甲醚辅助 Au(I)-硫醇盐合成途径；发现每个步骤的反应能都是负的。¹H NMR 计算用于表征不同金基序产生的环境如何影响二甘醇二甲醚上质子的化学位移，二甘醇二甲醚会经历强烈的低场位移。化学价的扩展过渡态-自然轨道 (ETS-NOCV) 理论也用于检查二甘醇二甲醚和金簇以及 Au ₂₀ (SR) ₁₅纳米簇之间的相互作用。我们的工作表明，二甘醇二甲醚可以在产生金纳米团簇的合成机制中发挥重要作用，并提供对二甘醇二甲醚-纳米团簇结合基序和由此产生的 NMR 化学位移的见解。

更新日期：2022-10-12

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