Toward Controlled Syntheses of Diphosphine-Protected Homochiral Gold Nanoclusters through Precursor Engineering

Controllable syntheses of Au nanoclusters (NCs) with different nuclearities are of great significance due to the kernel-dependent physicochemical properties. Herein, two pairs of enantiomeric Au NCs [Au₁₉(R/S-BINAP)₄(PhC≡C)Cl₄] (SD/Au19) and [Au₁₁(R/S-BINAP)₄(PhC≡C)₂]·Cl (SD/Au11), both with atropos (rigid axial chirality) diphosphine BINAP (2,2'-bis(diphenylphosphino)-1,1'-binaphthalene) as the predominant organic ligands, were controllably synthesized through precursor engineering. The former was obtained by direct reduction of HAuCl₄·4H₂O, while the latter was obtained by reduction of [Au(SMe₂)Cl] instead. Intriguingly, the kernel of SD/Au19 contains an Au₇ pentagonal bipyramid capped by two boat-like Au₆ rings, which represents another type of Au₁₉ kernel, making SD/Au19 a good candidate for comparative study with other Au₁₉ NCs to get more insight into the distinct structural evolution of phosphine-protected Au NCs. Despite the previous chiroptical studies on some other chiral undecagold NCs, the successful attainment of the X-ray crystal structures for SD/Au11 not only provides a step forward toward better correlating the chiroptical activities with their structural details but also reveals that even the auxiliary protecting ligands also play a nontrivial role in tuning the geometrical structures of the metal NCs. The chiroptical activities of both SD/Au19 and SD/Au11 were found to originate from the chiral ligands and core distortions; the extended π-electron systems in the BINAP ligands have proved to positively contribute to the electronic absorptions and thus disturb the corresponding circular dichroism (CD) responses.