Revealing the chirality origin and homochirality crystallization of Ag14 nanocluster at the molecular level

Abstract

Although chirality is an ever-present characteristic in biology and some artificial molecules, controlling the chirality and demystifying the chirality origin of complex assemblies remain challenging. Herein, we report two homochiral Ag14 nanoclusters with inherent chirality originated from identical rotation of six square faces on a Ag8 cube driven by intra-cluster π···π stacking interaction between pntp− (Hpntp = p-nitrothiophenol) ligands. The spontaneous resolution of the racemic (SD/rac-Ag14a) to homochiral nanoclusters (SD/L-Ag14 and SD/R-Ag14) can be realized by re-crystallizing SD/rac-Ag14a in acetonitrile, which promotes the homochiral crystallization in solid state by forming C–H···O/N hydrogen bonds with nitro oxygen atoms in pntp− or aromatic hydrogen atoms in dpph (dpph = 1,6-bis(diphenylphosphino)hexane) on Ag14 nanocluster. This work not only provides strategic guidance for the syntheses of chiral silver nanoclusters in an all-achiral environment, but also deciphers the origin of chirality at molecular level by identifying the special effects of intra- and inter-cluster supramolecular interactions.

Surface environment complication makes Ag29 nanoclusters more robust and leads to their unique packing in the supracrystal lattice

“…In the past two decades, silver nanoclusters have received unprecedented attention in cluster science. 25–40 It is widely accepted that silver nanoclusters exhibit promising functionalities and intriguing physical/chemical properties that are obviously different from their gold counterparts. 27 Ag-based metal nanoclusters generally display strong photoluminescence that renders them optically active nanomaterials for sensors or biological applications.…”

Asymmetric Twisting of C-Centered Octahedral Gold(I) Clusters by Chiral N-Heterocyclic Carbene Ligation

“…Asymmetric induction of molecular structures is expressed by intra- and intermolecular interactions and reactions and has contributed to the development of asymmetric catalysts, chromophores for chiral recognition, and chiroptical materials. − Gold cluster molecules protected by chiral ligands give rise to a unique chirality by the asymmetric rearrangement of gold atoms, − suggesting the importance of the linkage between the ligand and gold in chirality transfer. However, these studies have been limited primarily to bidentate ligation of staple-type bound thiolate ligands, biphosphines, − and diimido ligands because of their structural rigidity.…”

Conjugating AIE-featured AuAg nanoclusters with highly luminescent carbon dots for improved visible-light-driven antibacterial activity

“…[5][6][7][8] Therefore, developing long-lasting yet broad-spectrum antibacterials for public environment protection is highly desired. Recently, ultrasmall noble metal nanoclusters (NCs for short) with a core size of ≤3 nm as novel functional nanomaterials [9][10][11][12][13][14][15][16] have been demonstrated to be a new type of antibacterial agent, which features broad-spectrum antibacterial performance without inducing drug resistance of bacteria. [17][18][19][20][21] However, the conventional metal NC-based antibacterial agents mostly rely on their self-consumption (i.e., endocytosis of NCs or metal ions) to induce the generation of destructive reactive oxygen species (ROS) for bacterial killing, which constrains their longlasting antibacterial applications.…”