Diphosphine-induced chiral propeller arrangement of gold nanoclusters for singlet oxygen photogeneration

In this study, 1,2-bis(diphenylphosphino)ethane (dppe) ligands are used to synthesize gold nanoclusters with an icosahedral Au13 core. The nanoclusters are characterized and formulated as [Au13(dppe)5Cl2]Cl3 using synchrotron radiation X-ray diffraction, UV/Vis absorption spectroscopy, electrospray ionization mass spectrometry, and density functional theory (DFT) calculations. The bidentate feature of dppe ligands and the positions of coordinating surface gold atoms induce a helical arrangement that forms a propeller-like structure, which reduces the symmetry of the gold nanocluster to C1. Therefore, dppe ligands perform as a directing agent to create chiral an ansa metallamacrocycle [Au13(dppe)5Cl2]3+ nanocluster, as confirmed by simulated electronic circular dichroism spectrum. The highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap of the [Au13(dppe)5Cl2]3+ cluster is determined as approx. 1.9 eV, and further confirmed by ultraviolet photoemission spectroscopy analysis and DFT simulation. Furthermore, the photoactivity of [Au13(dppe)5Cl2]3+ is investigated, with the nanocluster shown to possess near-infrared photoluminescence properties, which can be employed for 1O2 photogeneration. The quantum yield of 1O2 photogeneration using the [Au13(dppe)5Cl2]3+ nanocluster is up to 0.71, which is considerably higher than those of anthracene (an organic dye), and Au25 and Au38 nanoclusters.