Assembly of silver(I)-copper(I) bimetallic thiolate complexes assisted by phenylacetylene stabilizers.

Ag/Cu bimetallic clusters have been widely reported, but synthesis of such clusters simple self-assembly of heterometallic ions in air remains challenging due to the susceptibility of Cu ions to oxidation. In this study, protected by the phenylacetylene auxiliary ligand, we utilized [Cu(CHCN)]PF in conjunction with the (PrSAg) polymer to form Ag(I)-Cu(I) oligomer precursors, serving as the starting point for constructing a new [AgCu(PrS)(DPPM)](PF) cluster (DPPM = bis(diphenylphosphino)methane, Ag11-xCux, = 5-9). When the (PrSAg) precursor was replaced by (BuSAg), another cluster [AgCuS(BuS)(CHCN)](CHOH)(HO)(PF) (Ag21Cu4) was obtained.

Theoretical analysis of naproxen reaction with sulfate and hydroxyl radicals in the aqueous phase: Investigating reactive sites and reaction kinetics.

In this study, we have utilized theoretical calculations to predict the reaction active sites of naproxen when reacting with radicals and to further study the thermodynamics and kinetics of the reactions with ·OH and SO. The evidence, derived from the average local ionization energy and electrostatic potential, points to the naphthalene ring as the preferred site of attack, especially for the C2, C6, C9, and C10 sites. The changes in Gibbs free energy and enthalpy of the reactions initiated by ·OH and SO ranged between -19.

Ag Cu (C=CAr) (DPPB) : A Rigid Ligand Co-Protected Bimetallic Silver(I)-Copper(I) Cluster with Room-Temperature Luminescence.

Metal clusters have become increasingly important in various applications, with ligands playing a crucial role in their construction. In this study, we synthesized a bimetallic cluster, Ag Cu (C=CAr) (DPPB) (Ag Cu ), using a rigid acetylene ligand, 3,5-bis(trifluoromethyl)phenylacetylide. Through single-crystal structure characterization, we discovered that the butterfly-shaped Ag Cu motifs were subject to distortion due to steric hindrance imposed by the rigid ligand.

Theoretical understanding of the effect of specifically adsorbed halide anions on Cu-catalyzed CO electroreduction activity and product selectivity.

Initial CO electroreduction into CO and its subsequent electroreduction pathways were selected to study the effect of specifically adsorbed halide anions X (X = F, Cl, Br, I) on CO electroreduction activity and product selectivity at Cu(111)/HO interfaces DFT calculations. The calculated results show that the presence of halide anions can exert a notable effect on the CO adsorption characteristics and that chemically adsorbed CO molecules can be formed. Furthermore, the halide-anion-modified Cu(111)/HO interfaces could significantly enhance the initial CO electroreduction into CO activity, which is regarded as the rate-determining step during CO electroreduction at clean Cu(111)/HO interfaces.

Theoretical insights into the electroreduction mechanism of N to NH from an improved Au(111)/HO interface model.

An improved H coverage-dependent Au(111)/HO electrochemical interface model is proposed in this paper, which is firstly used to study electroreduction mechanisms of N into NH at the thermodynamical equilibrium potential in cooperation with electronic structure analysis. The results show that the associative mechanism is more favorable on Au(111) and therein alternating and distal pathways may be able to parallelly occur in gas phase and the present simulated electrochemical interface. The initial N reduction into the NH intermediate is the rate determining step, which may be able to be regarded as the origin of the observed experimentally high overpotential during N electroreduction.

Support vector regression for high-resolution beach surface moisture estimation from terrestrial LiDAR intensity data.

Beach Surface Moisture (BSM) is a key attribute in the coastal investigations of land-atmospheric water and energy fluxes, groundwater resource budgets and coastal beach/dune development. In this study, an attempt has been made for the first time to estimate BSM from terrestrial LiDAR intensity data based on the Support Vector Regression (SVR). A long-range static terrestrial LiDAR (Riegl VZ-2000) was adopted to collect point cloud data of high spatiotemporal resolution on the Ostend-Mariakerke beach, Belgium.

Construction of Silver Clusters Capped by Zwitterionic Ethynide Ligands.

A zwitterionic ligand 3-(triethylammonio)propyne (TAP) has been employed to construct nine silver ethynide compounds for the first time. Single-crystal X-ray analyses reveal that compounds and are silver ethynide assemblies based on the Ag subunits and clusters - are small discrete clusters of Ag, Ag, Ag, and Ag, respectively, ligated by the bulky TAP ligand with different auxiliary ligands. In addition, upon acquiring the tripod-like BuPO, a unprecedented 80 nuclei silver ethynide cluster was isolated and determined to be [(CFCO)@Ag(TAP)(BuPO)(CFCO)] by crystallography and thermogravimetric analysis.

Controllable synthesis of porous tubular carbon by a Ag-ligand-assisted Stöber-silica/carbon assembly process.

Herein, in this study, we utilized Ag+-ligand interactions for critically regulating the morphology of carbon by the Stöber-silica/carbon co-assembly method for the first time. Tetraethyl orthosilicate (TEOS) and resorcinol/formaldehyde (RF) assemble upon dictation by Ag+ and pyridyl-functionalized surfactants, producing porous carbon tubes (RF1) with a high surface area of 696 m2 g-1 and accessible mesopores ∼15 nm in size. Furthermore, when using tetrapropyl orthosilicate (TPOS) with a slower hydrolysis rate than that of TEOS, carbon tubes (RF2) with enhanced uniformity and a surface area as high as 2112 m2 g-1 are generated.

Mechanistic insights into potential dependence of CO electrochemical reduction into C products based on a H coverage-dependent Cu(111)/HO interface model.

A H coverage-dependent Cu(111)/H2O interface model incorporated with electronic structure analysis is employed to investigate the potential dependence of CO electroreduction into C1 products with the aim of solving the long dispute over CO2 electrocatalytic reduction mechanisms. The results indicate that CH4 formation mainly proceeds through CO, CHO, CH2O, CH2OH and CHx (x = 2 and 3) species at various applied potentials. CH3OH may be formed via a CH3O intermediate at high overpotential and the present study can confirm that CH3OH is only produced in a trace amount as detected in experiments.

Density Functional Studies on Photophysical Properties of Boron-Pyridyl-Imino-Isoindoline Dyes: Effect of the Fusion.

In this work, to make out the aryl-fusion effect on the photophysical properties of boron-pyridyl-imino-isoindoline dyes, compounds - were theoretically studied through analyses of their geometric and electronic structures, optical properties, transport abilities, and radiative ( ) and non-radiative decay rate ( ) constants. The highest occupied molecular orbitals of aryl-fused compounds are higher owing to the extended conjugation. Interestingly, aryl fusion in pyridyl increases the lowest unoccupied molecular orbital (LUMO) level, while isoindoline decreases the LUMO level; thus, and with aryl fusion both in pyridyl and isoindoline exhibit a similar LUMO to .

-Butyl thiol and pyridine ligand co-protected 50-nuclei clusters: the effect of pyridines on Ag-SR bonds.

Constructing silver(i)-thiolate clusters from simple building blocks usually involves elusive self-assembly processes and remains a long-standing challenge. In this work, we report 6 silver(i)-thiolate clusters protected by pyridines, namely, [Ag3(tBuS)2(Py)(NO3)]n (Py = pyridine) (1), [Ag10(tBuS)6(Py)6(CF3CO2)4]·3Py (2), [Ag12(iPrS)6(Py)8(NO3)6]·2H2O (3), Ag12(iPrS)6(Py)8(CF3CO2)6 (4), Ag12(iPrS)6(4-ap)6(NO3)6 (4-ap = 4-aminopyridine) (5), and [Ag50S13(tBuS)20(Py)12]·4BF4·4Py·4CH3OH·2H2O (6). Single-crystal X-ray crystallography analysis reveals that six clusters are constructed by four types of structural blocks, including the PyAg(tBuS)2 monomer, Py2Ag2(tBuS)2 dimer, Py3Ag3(tBuS)3 trimer and (4-ap)6Ag6(iPrS)6 hexamer.

An in Situ Template for the Synthesis of Tunable Hollow Carbon Particles for High-Performance Lithium-Sulfur Batteries.

Nanostructured materials with hollow interior voids are gaining great attention due to their fantastic geometries and unique physicochemical properties competent for many applications. However, the development of a fast approach to prepare the hollow structured particles remains challenging. Herein, a new and efficient in situ hard-template method was developed to synthesize hollow carbon nano- and microparticles using the as-prepared SiO particles as a hard template directly, without any separation, drying, or redispersion.

Mechanistic study on Cu-catalyzed CO electroreduction into CH at simulated low overpotentials based on an improved electrochemical model.

An improved CO coverage-dependent electrochemical model with explicit relaxed H2O molecules used in CO2 electroreduction is presented, which is firstly applied to Cu-catalyzed CO2 electroreduction into CH4 production at low overpotentials in this paper. The results show that the present defined CH2O and CHOH pathways via common intermediates CHO and CH2 may be able to occur parallelly at the present simulated low overpotential. The potential-limiting steps may be the formation of CO and its further electroreduction into CHO, which are considered as the origin of the observed experimentally high overpotential.

Hybrid Rare-Earth(III)/Bismuth(III) Clusters Assembled with Phosphonates.

tert-Butylphosphonic acid and rare-earth precursors are employed to construct four trinuclear rare-earth phosphonate clusters, RE( BuPO)(hfac)(CHOH)]·2CHOH (RE = Eu, Y, Pr, and Sm; hfac = hexafluoroacetylacetonate), which are composed of three RE ions alternately bridged by two phosphonates. With the introduction of bismuth oxido diketonate, [BiO(hfac)], three different types of rare-earth/bismuth phosphonate clusters, BiRE (RE = Pr and Sm), BiEu, and BiY, are successfully obtained via variation of the reaction conditions, and they are the first reported examples of bismuth-oxo clusters encapsulated by cyclic rare-earth-oxo or rare-earth/bismuth-oxo phosphonate clusters, respectively. These clusters show obvious absorption in the UV region, and the Eu-containing clusters exhibit bright-red fluorescence.

A theoretical investigation on the thermally activated delayed fluorescence characteristics of the isomers of DTCBPy.

It has been reported that 3, 5-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)-phenyl)(pyridin-4-yl)meth (DTCBPy) is an efficient thermally activated delayed fluorescence (TADF) molecule. We designed a series of the isomeric molecules (2-5) of DTCBPy (1) by changing the position of nitrogen atom in the acceptor and the substituent position of donor units. The highest occupied molecular orbitals (HOMO) of 1-5 are all delocalized over the donor units, and the lowest unoccupied molecular orbitals (LUMO) are located on the acceptor unit.

High-nuclearity silver ethynide clusters containing polynucleating oxygen donor ligands.

Polynucleating oxygen donor ligands as precursors have been employed to construct three high-nuclearity heterometallic ethynide clusters. Compound 2 consists of a Cl@Ag ethynide cluster capped by two trinuclear organooxotin phosphonate clusters [(BuSn)(μ-O)(BuPO)(OMe)(OH)]. Compound 3 consists of a Ag ethynide cluster fused with a nonanuclear oxo-bismuth phosphonate cluster [BiO(BuPO)(BuPOH)], while compound 4 is composed of two Cl@Ag ethynide clusters bridged by a hexanuclear oxo/hydroxo-bismuth phosphonate cluster [BiO(OH)(BuPO)(hfac)(CFCOO)].

High-Nuclearity Heterometallic tert-Butylethynide Clusters Assembled with tert-Butylphosphonate.

tert-Butylphosphonic acid and lanthanide precursors were employed to construct two high-nuclearity hybrid silver(I)-ytterbium(III) phosphonate clusters: compound 1 consists of a Ag ethynide cluster fused with a trinuclear hydroxoytterbium phosphonate cluster, whereas compound 2 is composed of two Ag ethynide clusters bridged by a hexanuclear oxo/hydroxoytterbium phosphonate cluster. Using transition-metal-substituted lacunary polyoxotungstates in place of the lanthanide reactant, new phosphonate-functionalized silver(I)-copper(II) ethynide clusters [Ag Cu (3) and Ag Cu (4)] and silver(I) ethynide clusters [Ag (5) and Ag (6)] were obtained. The structures of complexes 3-6 feature core-shell arrangements, in which silver(I)-copper(II) or silver(I) ethynide cluster shells stabilized by peripheral phosphonate ligands enclose different kinds of tungstate core templates.

A simple fluorescent probe for the fast sequential detection of copper and biothiols based on a benzothiazole derivative.

A simple benzothiazole fluorescent chemosensor was developed for the fast sequential detection of Cu and biothiols through modulating the excited-state intramolecular proton transfer (ESIPT) process. The compound 1 exhibits highly selective and sensitive fluorescence "on-off" recognition to Cu with a 1:1 binding stoichiometry by ESIPT hinder. The in situ generated 1-Cu complex can serve as an "on-off" fluorescent probe for high selectivity toward biothiols via Cu displacement approach, which exerts ESIPT recovery.

Structure-Directing Role of Phosphonate in the Synthesis of High-Nuclearity Silver(I) Sulfide-Ethynide-Thiolate Clusters.

Phosphonate ligands as structure-directing components have been employed to construct four new high-nuclearity silver(I) sulfide-ethynide-thiolate clusters, in which silver(I) aggregates BuC≡C⊃Ag, BuC≡C⊃Ag, and 2BuC≡C⊃Ag are bridged by BuS ligands to engender respective silver(I) ethynide-thiolate clusters functioning as integral shell components, which are supported by phosphonate ligands. In each silver(I) sulfide-ethynide-thiolate cluster, a different encapsulated silver sulfide cluster serves as a core template.

A new simple phthalimide-based fluorescent probe for highly selective cysteine and bioimaging for living cells.

A new turn-on phthalimide fluorescent probe has designed and synthesized for sensing cysteine (Cys) based on excited state intramolecular proton transfer (ESIPT) process. It is consisted of a 3-hydroxyphthalimide derivative moiety as the fluorophore and an acrylic ester group as a recognition receptor. The acrylic ester acts as an ESIPT blocking agent.

High-Nuclearity Silver Thiolate Clusters Constructed with Phosphonates.

The n-butylphosphonate ligand has been employed to construct three new silver(I) thiolate compounds. Single-crystal X-ray analysis revealed that complexes 1 and 2 are Ag48 and Ag51 coordination chain polymers, while 3 contains a discrete Ag48 cluster, in which three different kinds of silver(I) thiolate cluster shells enclose three different phosphonate-functionalized silver(I) cluster cores, respectively. The structures of clusters in 1-3 feature three three-shell arrangements, S@Ag12 @(nBuPO3 )9 @Ag36 S23 , S@Ag11 @(nBuPO3 )7 (MoO4 )2 @Ag40 S27 and MoO4 @Ag12 @(nBuPO3 )8 S6 @Ag36 S24 , respectively.

Density functional studies on photophysical properties and chemical reactivities of the triarylboranes: effect of the constraint of planarity.

The geometric and electronic structures, absorption spectra, transporting properties, chemical reactivity indices and electrostatic potentials of the planar three-coordinate organoboron compounds 1-2 and twisted reference compound Mes(3)B, have been investigated by employing density functional theory (DFT) and conceptual DFT methods to shed light on the planarity effects on the photophysical properties and the chemical reactivity. The results show that the planar compounds 1-2 exhibit significantly lower HOMO level than Mes(3)B, owing to the stronger electronic induction effect of boron centers. This feature conspicuously induces a blue shifted absorption for 1, although 1 seemingly possesses more extended conjugation framework than Mes(3)B.