Exceptionally Stable Dimers and Trimers of Au₂₅ Clusters Linked with a Bidentate Dithiol: Synthesis, Structure and Chirality Study

Abstract

A bidentate chiral dithiol (diBINAS) is utilised to bridge Au 25 nanoclusters to form oligomers. Separation by size allows the isolation of fractions that are stable thanks to the bidentate nature of the linker. The structure of the products is elucidated by smallangle X-ray scattering and calculated using density functional theory. Additional structural details are studied by diffusion-ordered nuclear magnetic resonance spectroscopy, transmission electron microscopy and matrix-assisted laser desorption/ionization time of flight mass spectrometry. Significant changes in the optical properties are analysed by UV/Vis and fluorescence spectroscopies, with the latter demonstrating a strong emission enhancement. Furthermore, the emergent chiral characteristics are studied by circular dichroism. Due to the geometry constraints of the nanocluster assemblies, diBINAS can be regarded as a templating molecule, taking a step towards the directed selfassembly of metal clusters.

Diphosphine‐Protected IrAu12 Superatom with Open Site(s): Synthesis and Programmed Stepwise Assembly

“…[5][6][7][8][9] In order to assemble Au CMSs via covalent bonding, ligand exchange reactions with multidentate ligands have been frequently used. [10][11][12][13] However, design and fabrication of controlled assembled structures are challenging because the number and position of exchangeable sites of Au CMSs are difficult to control. A promising approach to overcome this problem is to preinstall exposed sites on the Au CMSs whereby the Au CMSs are assembled into a programmed structure by multidentate ligands.…”

Visible to NIR‐II Photoluminescence of Atomically Precise Gold Nanoclusters

“…The captivating photoluminescence (PL) properties of atomically precise gold NCs lie at the core of the research and have attracted extensive interest. [2,[9][10][11][12][13][14][15][16][17] These luminescent NCs DOI: 10.1002/adma.202309073 are found to exhibit emission peaks ranging from the visible to the nearinfrared (NIR) region (Scheme 1, 500 to 1700 nm), [18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33] and NIR-II luminescence (1000-1700 nm) is of particular interest in recent research. [34][35][36][37][38][39] Such a broad range of emission wavelengths of gold NCs is unparalleled by other luminescent materials such as dyes and metal complexes.…”

Restriction of intramolecular rotation for functionalizing metal nanoclusters

“…1,2 Besides, metal clusters or cluster-based nanomaterials display intriguing physicochemical properties that can be rationalized in terms of their discrete electronic states and quantum size effects. 7–16 In addition, such properties ( e.g. , optical, electrochemical, magnetic, and chiral properties) show a clear relationship with cluster structures, and any perturbations in their compositions/constructions will induce tremendous changes in properties.…”

“…1,2 Besides, metal clusters or cluster-based nanomaterials display intriguing physicochemical properties that can be rationalized in terms of their discrete electronic states and quantum size effects. [7][8][9][10][11][12][13][14][15][16] In addition, such properties (e.g., optical, electrochemical, magnetic, and chiral properties) show a clear relationship with cluster structures, and any perturbations in their compositions/constructions will induce tremendous changes in properties. [17][18][19][20][21][22][23][24] In this context, the atomically precise nature of nanoclusters facilitates structure-property correlation elucidation, making them remarkably useful for the rational customization of cluster-based nanomaterials with tailored performance.…”