Anion-Directed Assembly of a Bimetallic Pd/Ag Nanocluster: Synthesis, Characterization, and HER Activity.

Palladium-doped silver nanoclusters (NCs) have been highlighted for their unique physicochemical properties and potential applications in catalysis, optics, and electronics. Anion-directed synthesis offers a powerful route to control the morphology and properties of these NCs. Herein, we report a novel Pd-doped Ag NC, [Pd(H)Ag(S){SP(OPr)}] (), synthesized through the inclusion of sulfide and hydride anions.

A living library concept to capture the dynamics and reactivity of mixed-metal clusters for catalysis.

The exploration of ligated metal clusters' chemical space is challenging, partly owing to an insufficiently targeted access to reactive clusters. Now, dynamic mixtures of clusters, defined as living libraries, are obtained through organometallic precursor chemistry. The libraries are populated with interrelated clusters, including transient and highly reactive ones, as well as more accessible but less reactive species.

Hydride-containing Ag- and Au-rich 8-electron superatomic icosahedral cores: a DFT investigation.

Following several reports on ligand-protected atom-precise nanoclusters which encapsulate hydrides as interstitial dopants within their icosahedral core, the stability, structure and bonding of MH@Ag and MH@Au (M = Mo-Ag; W-Au) 8-electron cores is investigated through DFT calculations. The encapsulation of up to = 3 hydrides appears to be possible but at the cost of substantial structural distortions. In most of the computed models, the hydrides are found nearly free to move inside their icosahedral cages.

Sulfide-mediated growth of NIR luminescent Pd/Ag atomically precise nanoclusters.

An essential feature of coinage metal nanoclusters (NCs) is their photoluminescence (PL), which spans a wide range of wavelengths from visible to near-infrared regions (NIR-I/II). A key challenge for synthetic chemists is to develop materials capable of efficient spectral change with maximum efficiency. Herein, we report novel dithiolate-protected bimetallic Pd-Ag NCs of the type [PdAgS{SP(OR)}] (R = Pr, 1Pr and Bu, 1Bu) and [PdAgS{SP(OBu)}] (2Bu).

Cuboctahedral Pd as a spherical aromatic noble metal core: insights from a ligand-protected [Pd(Tr)] cluster.

Low-valent palladium nanoparticles are efficient species promoting catalytic activity and selectivity in a number of chemical reactions. Recently, an atom-centered cuboctahedral Pd motif has been characterized as a ligand-protected [Pd(Tr)] cluster featuring a 1s superatomic shell structure. In this report, we describe the ligand-cluster of and endohedral-cage interaction in [Pd(Tr)], which accounts for a favorable situation in the overall cluster.

Cuprophilic Interactions in Polymeric [CuO(Mes)].

The properties of cuprophilic compounds and the underlying fundamental principles responsible for the Cu(I)···Cu(I) interactions have been the subject of intense research as their diverse structural and physical attributes are being explored. In this light, we performed a new study of the compound [CuO(Mes)] reported by Haakansson et al. using state of the art experimental and theoretical analysis techniques.

Controlled aggregation of Pt/PtH/Rh/RhH doped silver superatomic nanoclusters into 16-electron supermolecules.

The assembly of discrete superatomic nanoclusters into larger constructs is a significant stride towards developing a new set of artificial/pseudo-elements. Herein, we describe a novel series of 16-electron supermolecules derived from the combination of discrete 8-electron superatomic synthons containing interstitial hydrides as vertex-sharing building blocks. The symmetric (RhH)Ag[SP(OPr)] (1) and asymmetric PtHPtAg[SP(OPr)] (2) are characterized by ESI-MS, SCXRD, NMR, UV-vis absorption spectra, electrochemical and computational methods.

C-H bond activation at antimony(III): synthesis and reactivity of Sb(III)-oxyaryl species.

We report on the synthesis, structure and reactivity of [{NCN}Sb(CH-Bu-3,5-O-4)] (3), an organoantimony(III)-oxyaryl species obtained upon C-H bond activation in a phenolate ligand and stabilised by the monoanionic pincer {NCN}. The mechanism leading to the formation of 3 is highly sensitive to steric considerations. It was probed experimentally and by DFT calculations, and a number of intermediates and related complexes were identified.

Barium phosphidoboranes and related calcium complexes.

The attempted synthesis of [{Carb}BaPPh] (1) showed this barium-phosphide and its thf adducts, 1·thf and 1·(thf), to be unstable in solution. Our strategy to circumvent the fragility of these compounds involved the use of phosphinoboranes HPPh·BH and HPPh·B(CF) instead of HPPh. This allowed for the synthesis of [{Carb}Ae{PPh·BH}] (Ae = Ba, 2; Ca, 3), [{Carb}Ca{(HB)PPh}·(thf)] (4), [{Carb}Ba{PPh·B(CF)}] (5), [{Carb}Ba{O(B(CF))CHCHCHCHPPh}·thf] (6), [Ba{O(B(CF))CHCHCHCHPPh}·(thf)] (7) and [Ba{PPh·B(CF)}·(thp)] (8) that were characterised by multinuclear NMR spectroscopy (thp = tetrahydropyran).

Doping effect on a two-electron silver nanocluster.

This study investigates the effects of metal addition and doping of a 2-electron silver superatom, [Ag{SP(OPr)}] (Ag10). When Ag is added to Ag10 in THF solution, [Ag{SP(OPr)}(OTf)] (Ag11) is rapidly formed almost quantitatively. When the same method is used with Cu, a mixture of alloys, [CuAg{SP(OPr)}] ( = 1-3, CuxAg11-x), is obtained.

Assignment of individual structures from intermetalloid nickel gallium cluster ensembles.

Poorly selective mixed-metal cluster synthesis and separation yield reaction solutions of inseparable intermetalloid cluster mixtures, which are often discarded. High-resolution mass spectrometry, however, can provide precise compositional data of such product mixtures. Structure assignments can be achieved by advanced computational screening and consideration of the complete structural space.

Atom-Precise Ligated Copper and Copper-Rich Nanoclusters with Mixed-Valent Cu(I)/Cu(0) Character: Structure-Electron Count Relationships.

Copper homometallic and copper-rich heterometallic nanoclusters with some Cu(0) character are reviewed. Their structure and stability are discussed in terms of their number of "free" electrons. In many aspects, this structural chemistry differs from that of their silver or copper homologs.

All-Hydrocarbon-Ligated Superatomic Gold/Aluminum Clusters.

Key strategies in cluster synthesis include the use of modulating agents (e.g., coordinating additives).

Diselenophosphate Ligands as a Surface Engineering Tool in PdH-Doped Silver Superatomic Nanoclusters.

The first hydride-doped Pd/Ag superatoms stabilized by selenolates are reported: [PdHAg(dsep)] [dsep = SeP(OPr)] and [PdHAg(dsep)] . was derived from the targeted transformation of [PdHAg(dtp)] [dtp = SP(OPr)] by ligand exchange, whereas was obtained from the addition of trifluoroacetic acid to , resulting in a symmetric redistribution of the capping silver atoms. The transformations are all achieved while retaining an 8-electron superatomic configuration.

Hydride-Containing Pt-doped Cu-rich Nanoclusters: Synthesis, Structure, and Electrocatalytic Hydrogen Evolution.

A structurally precise hydride-containing Pt-doped Cu-rich nanocluster [PtH Cu {S P(O Pr) } (CCPh) ] (1) has been synthesized. It consists of a bicapped icosahedral Cu cage that encapsulates a linear PtH unit. Upon the addition of two equivalents of CF COOH to 1, two hydrido clusters are isolated.

Observational and prospective study: evaluation of beliefs and representations of chronic treatments of polymedicated patients hospitalised in a vascular medicine and surgery department.

Objectives: Today, the involvement of patients in their care is essential. As the population ages increases, the number of patients with chronic diseases is increasing. In the vascular medicine and surgery departments, patients are polymedicated and mostly suffer from several chronic diseases.

Hydride Doping Effects on the Structure and Properties of Eight-Electron Rh/Ag Superatoms: The [RhH@Ag{SP(OPr)}] ( = 0-2) Series.

Three hitherto unknown eight-electron rhodium/silver alloy nanoclusters, [RhAg{SP(OPr)}] (), [RhHAg{SP(OPr)}] (), and [RhHAg{SP(OPr)}] (), have been isolated and fully characterized. Cluster contains a regular Rh@Ag icosahedral core, whereas and exhibit distorted RhH@Ag and RhH@Ag icosahedral cores. The single-crystal neutron structure of located the encapsulated hydride at the center of an enlarged RhAg tetrahedron.

A heteroleptic fused bi-cuboctahedral Cu21S2 cluster.

A new dicationic cluster, [CuS{SCNBu}(CPh)], where the Cu21S2 kernel consists of two S@Cu cuboctahedra sharing a triangular Cu face is reported. Its waist part is bridged by three dithiocarbamate ligands, each in a hexaconnective, hexametallic (μ, μ) coordination pattern, an unprecedented feature in Cu nanocluster chemistry.

Metal-Metal Bonding in Late Transition-Metal [ML] Complexes: Exploring the Limits of the Isolobal Analogy between the CO and AlCp* Ligands.

Late dinuclear transition-metal (especially group 10 and 11) homoleptic carbonyl complexes are elusive species and have so far not been isolated. A typical example is the 30-electron species [Ni(CO)], the structure and bonding of which is still debated. We show that, by using the AlCp* ligand (isolobal to CO), it is possible to isolate and fully characterize [Ni(AlCp*)] (), which inspired us to revisit by DFT calculations, the bonding situation within [NiL] (L = CO, AlCp*) and other isoelectronic species.

Catalytic Alkyne Semihydrogenation with Polyhydride Ni/Ga Clusters.

The bimetallic, decanuclear Ni Ga -cluster of the formula [Ni (GaTMP) (μ -GaTMP) (μ -GaTMP)] (1, TMP=2,2,6,6-tetramethylpiperidinyl) reacts reversibly with dihydrogen under the formation of a series of (poly-)hydride clusters 2. Low-temperature 2D NMR experiments at -80 °C show that 2 consist of a mixture of a di- (2 ), tetra- (2 ) and hexahydride species (2 ). The structures of 2 and 2 are assessed by a combination of 2D NMR spectroscopy and DFT calculations.

Ensuring quality control in a COVID-19 clinical trial during the pandemic: The experience of the Inserm C20-15 DisCoVeRy study.

Setting: Health measures taken during the pandemic deeply modified the clinical research practices. At the same time, the demand for the results of the COVID-19 trials was urgent. Thus, the objective of this article is to share Inserm's experience in ensuring quality control in clinical trials in this challenging context.

Exploration of the barriers and enablers of benzodiazepines deprescribing in prisons: A qualitative study among health and social care professionals.

Background: The prison environment is a place of high consumption of benzodiazepines (BZDs) due to the anxiety and sleep disturbances, mental disorders, detoxification and trafficking.

Objective: The study aims to explore experiences of health and social care professionals on the use of BZDs in prisons, as well as the barriers and enablers to their deprescribing.

Method: Semistructured individual interviews with professionals working in a prison setting were performed between March and April 2022, based on an interview guide.

Monocarboxylate-protected two-electron silver nanoclusters with high photothermal conversion performance.

The first series of monocarboxylate-protected silver nanoclusters was synthesized and fully characterized by X-ray diffraction, fourier-transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and electrospray ionization mass spectrometry (ESI-MS). Specifically, compounds [Ag(L)(9-AnCO)] (L = PhP (I), (4-ClPh)P (II), (2-furyl)P (III), and PhAs (IV)) were prepared by a solvent-thermal method under alkaline conditions. These clusters exhibit a similar unprecedented structure containing a [Ag@Ag] metal kernel, of which the 2-electron [Ag] inner core shows a flattened and puckered hexagonal bipyramid of symmetry.