Alkynyl-protected gold clusters have recently gained attention as they have been found to be more structurally versatile compared to their thiolate protected counterparts. In 2019, Tsukuda, T. et al. showed that the π−Au−π bonds work as a flexible joint between the rigid (σ,σ) units to release the strain in Au22(C<b>≡</b>CR)18 clusters. The group synthesized clusters with R = ETP, PA and ET, (ETP = 3-ethynylthiophene, PA = Phenylacetylene, ET = 3-ethynyltouluene) and found that while the choice of R group does not change the geometric and electronic structure, the PL mechanism is highly dependent upon this choice. In this work, we benchmark the geometric/electronic, optical and photoluminescent properties of Au22(C<b>≡</b>CR)18 for R = ETP, PA and ET by exploring solvent and dispersion effects, basis set size and exchange-correlation functionals.

Theoretical benchmarking of the R-dependent photoluminescence in alkynyl-protected Au22 nanoclusters using TDDFT and TDDFT+TB

ACS Fall 2021

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