A novel 58-nuclei silver nanowheel encapsulating a subvalent Ag64+ kernel

The combination of CrO4^2-anion and N,N′-dimethylformamide(DMF)-containing solvent helps to stabilize an atom-precise ultrasmall Ag6 kernel into a 52-nuclei silver shell,giving a core-shell Ag6@Ag52 wheel-like structure(SD/Ag58b).The solution behavior and photocurrent response property were investigated in details.

In Situ Capture of a Ternary Supramolecular Cluster in a 58-Nuclei Silver Supertetrahedron

Although inorganic anion templates are highly appreciated in the synthesis of nanosized silver clusters,supramolecular clusters used as templates to mold silver nanoclusters remain as-yet-unknown due to their existence as volatile forms in solution.Here,we report the synthesis of a novel silver-thiolate nanocluster(SD/Ag58a),comprising an outer tetrahedral cage of 58 silver atoms and a central supramolecular cluster[CH_(3)OH@(SO_(4))_(4)(H_(2)O)6]8−(hereafter abbreviated as CS_(4)H_(6)).Ternary CS_(4)H_(6) cluster was constructed from an(SO_(4))_(4) tetrahedron encaging one CH_(3)OH molecule inside and six water molecules sitting between paired SO_(4)^(2−)ions to form the[SO_(4)…H_(2)O…SO_(4)]hydrogen bonds(H-bonds).Also,the CS4H6 could coordinate to the inner wall of the Ag58 cage by forming Ag-O bonds,exerting templating effect on the formation of SD/Ag58a.Moreover,SD/Ag58a showed a photocurrent response upon visible light irradiation and emitted luminescence in the near-infrared(NIR)region at a cryogenic temperature.This work exemplifies the ternary supramolecule templating effect in the construction of silver nanocluster and facilitates understanding of the structure of complex solvated anion cluster in atomic precision.

Carbonate-Water Supramolecule Trapped in Silver Nanoclusters Encapsulating Unprecedented Ag_(11) Kernel

In the absence of inorganic anion templates and in high pH condition(pH∼14),an unprecedented carbonate-hydrate supramolecule,[(CO_(3))_(2)(H_(2)O)]^(4−),trapped from atmospheric CO_(2),found to play an anion templating role to support the architecture of two related silver(Ag)nanoclusters(SD/Ag54a and SD/Ag55a),which are coprotected by the same organic ligands but differ by one silver atom of the metallic frameworks.Two[(CO_(3))_(2)(H_(2)O)]^(4−)supramolecules are trapped into two Ag/tBuPhS/dppm pods,connected by a pair of face-shared silver pentagonal bipyramids(Ag_(11))into peanut-shaped silver nanoclusters.Interestingly,the equatorial Ag_(11) kernel represents a new embryonic ultrasmall silver nanocluster that is thought to follow a special facesharing growth fashion from pentagonal bipyramidal Ag7 subunit,which is also structurally elucidated in another new Ag44 nanocluster(SD/Ag44c)obtained in similar assembly system just changing tBuPhS−to iPrPhS−ligand.The isolation of SD/Ag54a and SD/Ag55a were associated with:(1)supramolecule induction and(2)reductive and carbonate-rich assembly system.First,this work brings a fresh perspective on the role of carbonate-water anion supramolecule in directing the assembly of silver nanoclusters.Second,it realizes the control of reduction kinetics and kernel growth using multiple weak reductants and thiolate ligands.Third,it provides a possible face-shared growth route for ultrasmall silver nanoclusters.

Sniffing with mass spectrometry

Gaseous compounds are usually on-line detectable on sensors. The limitations of conventional sensors are suffering from incapability for exactly identifying multiple components as well as incompatibility to possible toxicants in every odor sample. Herein, we discuss an inlet modification to the laboratory standard mass spectrometer, inspired by the sensitive olfactory systems of animals, for direct sniffing,established by connecting a mini pump to the nebulizer gas tubing. The modified mass spectrometry method—sniffing-mass spectrometry(sniffing-MS)—can acquire detailed fingerprint spectra of mixed odors and shows high tolerance to toxicants. Furthermore, the method has a low limit of detection in the order of parts per trillion and is a ‘sampling-free' technique for analyzing various gaseous compounds simultaneously, thus offering versatility for smelling daily commodities, tracking diffusion, and locating position of odors. Sniffing-MS can mimic or even surpass the olfaction of animals and is applicable for analyzing gaseous/volatile compounds, especially those polar compounds, in a simple manner depending on the intrinsic molecular mass-to-charge ratio.