Addition Reaction-Induced Cluster-to-Cluster Transformation: Controlled Self-Assembly of Luminescent Polynuclear Gold(I) μ₃-Sulfido Clusters

Abstract

Unprecedented addition reaction-induced gold(I) cluster-to-cluster transformation has been observed in the present work. Reaction of the chlorogold(I) precursor, [vdpp(AuCl)2] (vdpp = vinylidenebis(diphenylphosphine)) containing the diphosphine with unsaturated C═C bond, with H2S resulted in a series of polynuclear gold(I) μ3-sulfido clusters bearing Au(I)···Au(I) interactions; the identities of which have been fully characterized by NMR, electrospray-ionization mass spectrometry, elemental analysis, and single crystal X-ray diffraction analysis. Diverse research methods, including UV-vis absorption, (1)H NMR, and (31)P NMR spectroscopy, were employed to detect and monitor the transformation and assembly processes. Supported by single crystal structures, the existence of Au(I)···Au(I) bonding interactions sustains the diverse array of sophisticated polynuclear cluster structures and endues them with rich luminescence features.

Self‐Assembly of Chiral Gold Clusters into Crystalline Nanocubes of Exceptional Optical Activity

“…Stokes shift of approximately 138 nm clearly suggest that the luminescence of clusters originates from at riplet parentage, which is assigned to at riplet ligand-to-metal charge transfer ( 3 LMCT) excited state or at riplet ligand-to-metal-metal charge transfer ( 3 LMMCT) excited state. [15] It needs to be stressed that based on the facts of 2.676(2) AuÀAu bond length and the mixed-valence of Au (0/I), the attractive aurophilic interaction should considerably contribute to the PL properties of chiral Au clusters. [16] More intriguingly,these chiral Au cluster assemblies show strong CPL response in the same wavelength region as their PL peak centered at 583 nm (Figure 3c).…”

“…The dominant PL decay time also follows the order: 50 % n ‐hexane (0.59 μs) <60 % n ‐hexane (0.69 μs) <70 % n ‐hexane (0.79 μs) >80 % n ‐hexane (0.75 μs) >90 % n ‐hexane (0.68 μs) (Figure S7). The microsecond PL decay time and the large Stokes shift of approximately 138 nm clearly suggest that the luminescence of clusters originates from a triplet parentage, which is assigned to a triplet ligand‐to‐metal charge transfer ( 3 LMCT) excited state or a triplet ligand‐to‐metal‐metal charge transfer ( 3 LMMCT) excited state . It needs to be stressed that based on the facts of 2.676(2) Å Au−Au bond length and the mixed‐valence of Au (0/I), the attractive aurophilic interaction should considerably contribute to the PL properties of chiral Au clusters .…”

Self‐Assembly of Chiral Gold Clusters into Crystalline Nanocubes of Exceptional Optical Activity

“…[15] It needs to be stressed that based on the facts of 2.676(2) AuÀAu bond length and the mixed-valence of Au (0/I), the attractive aurophilic interaction should considerably contribute to the PL properties of chiral Au clusters. [15] It needs to be stressed that based on the facts of 2.676(2) AuÀAu bond length and the mixed-valence of Au (0/I), the attractive aurophilic interaction should considerably contribute to the PL properties of chiral Au clusters.…”

Aurophilicity‐Mediated Construction of Emissive Porous Molecular Crystals as Versatile Hosts for Liquid and Solid Guests

“…[13] However, Au···Au interactions have not yet been employed for the construction of organic porous materials. [14] Our group has comprehensively investigated as eries of aryl gold isocyanide complexes with tunable emission properties, polymorphism, and phase transitions. [15] We proposet hat porousc rystals that are formed due to Au···Au interactions between gold isocyanide complexes should exhibit versatile responsive behavior of their emission that depends on the nature of the small guest molecules in their cavities.A fter extensive screenings of gold isocyanide complexes and their crystallization conditions, we found that the bent aryl gold isocyanide complex 1 [16] (Figure 1) forms an extrinsicp orousm aterial due to the manifestation of prominent Au···Au interactions.…”