Effects of Diglyme on Au Nanocluster Formation: Mechanism, 1 H NMR, and Bonding.

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. 1 H 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 Au 20 (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.