Journal of Cluster Science

The clusters [H2Os4M(CO)12eta6-C6H6)] (M=Os, Ru) may be deprotonated to generate anions [Os4M(CO)12eta6-C6H6)]2- which react with [M′eta6-C6H5R) (MeCN)3]2+(M′=Os, Ru; R=H, Me) to give the bicapped tetrahedral clusters [Os4(CO)12MM′eta6-C6H5R)2]. Whereas [Os4(CO)12M2eta6-C6H6)2] (M=Os, Ru) have one Meta6-C6H6) unit in a site connected to three other metals, {3}, and one in a site connected to four other metals, {4}, [Os4(CO)12OsRueta6-C6H6)2] has the Rueta6-C6H6) unit in the {3} site irrespective of whether the Os or Ru anion is capped. Coupling of these anions with Au2dppm yields [Os4M(CO)12eta6-C6H6)(Au2dppm)] (M=Os, Ru), which have the arene ligand in the axial site of a trigonal bipyramid and the digold unit capping two faces. Reduction of [H2Os5(CO)15] with K/Ph2CO and coupling with [Rueta5-C5H5)(MeCN)3]2+yields the monoanion [Os5(CO)15Rueta5-C5H5)]− which reacts with [AuPPh3]+ generating [Os5(CO)15Rueta5-C5H5)(AuPPh3)] with the “Ru(C5H5)” unit in the terminal {3} site.

The cytotoxic properties of cobalt oxide (Co3O4) nanoparticles (NPs), in addition to graphene oxide (GO)-Co3O4 and silver (Ag)-GO-Co3O4 nanocomposites (NCs), were evaluated against both human healthy lung fibroblast (MRC-5) and hepatocellular carcinoma (HepG2) cell lines utilizing the XTT assay. The investigation revealed that synthesized Co3O4 NPs and NCs (GO-Co3O4 and Ag-GO-Co3O4) elicited significant cytotoxic responses in MRC-5 and HepG2 cell lines in a concentration-dependent manner. Through molecular docking analyses, it was observed that all fabricated nanomaterials exhibited DNA recognition via minor groove binding, with molecular affinities ranging from − 4.82 to -11.66 kcal/mol. Furthermore, the docking outcomes illustrated that the angular conformations of GO-Co3O4 and Ag-GO-Co3O4 conferred ‘shape-selective’ characteristics as DNA minor groove binders, leading to heightened cytotoxicity, particularly in the HepG2 cell line compared to the normal MRC-5 cell line.

The adsorption and decomposition of formic acid (HCOOH) on pristine and carbon doped B12N12 nanocage are investigated using density functional theory calculations. Both dehydration and dehydrogenation pathways of HCOOH are considered. Based on the present theoretical results, B11N12C nanocage can effectively decompose the HCOOH molecule with the C atom as an activation site, and the corresponding activation energy barriers for the dehydrogenation and dehydration are significantly lowered, compared with the undoped B12N12 case. The catalytic activity of the B11N12C for formic acid dehydrogenation is explored and the calculated barrier (28.2 kcal/mol) of the reaction HCOO → CO2 + H is lower than those on the traditional noble metals. Our results reveal that the low cost B11N12C can be used as an effective metal-free catalyst for HCOOH decomposition at ambient temperature.

The Becke’s three parameter hybrid change functional based on the density functional theory method is used to investigate the magnetic transition of Tcn (n = 1, 2) induced by the reaction with Cl and BO2. Simply, the two Tc atoms in the Tc2 dimer are FM coupled, but undergoes antiferromagnetic transition when ionized to the Tc 2 + state. Interestingly, both Cl and BO2, due to their highly electronegative character, can draw electrons from the Tc2 dimer, leaving them in cationic states, therefore, the antiferromagnetic transition can also be induced when Tcn (n = 1, 2) reacts with Cl or BO2. The two Tc atoms are antiferromagnetic coupled in the neutral Tc2Cl, Tc2BO2, (Tc2Cl)2, and anionic (Tc2Cl)2, however are ferromagnetic coupled in Tc2Cl− and Tc2BO2 −. The ability to induce a magnetic transition through a chemical reaction provides a way to synthesize new magnetic materials.

The reaction of Fe2(CO)9 and Bu 3 t SnH yielded the bimetallic cluster complexes Fe2(μ-SnBu 2 t )2(CO)8, 1, and Fe4(μ4-Sn)(μ-SnBu 2 t )2(CO)16, 3. Compound 3 contains two Fe2(CO)8(μ-SnBu 2 t ) groups held together by a central quadruply bridging tin atom, giving an overall bow-tie structure for the one tin and four iron atoms. Refluxing compound 1 in toluene solvent affords the complex Fe2[μ-SnBut(CH2Ph)]2(CO)8, 4, where two of the But groups in 1 have been replaced with benzyl groups, as a result of selective benzylic C–H bond activation of solvent toluene. Similarly refluxing compound 1 in ortho-, meta- and para-xylene solvents gives the complexes where two, three and four of the But groups in 1 have been replaced by the respective xylyl groups. Compound 1 also reacts with ethylbenzene to furnish the complex Fe2[μ-SnBut(MeCHPh)]2(CO)8, 14, where two of the But groups in 1 have been replaced as a result of the benzylic C–H activation of ethylbenzene. A mechanism based on a radical pathway is proposed for the selective C–H bond activation by 1.

β- and α-phase porous Bi2O3 microspheres with an average size of around 4 μm had been synthesized by thermal treatment of Bi2O2CO3 microspheres at 350 and 400–500 °C respectively in an air atmosphere. The Bi2O2CO3 microspheres had been synthesized at a temperature of 180 °C by a hydrothermal process using Bi(NO3)3 as the bismuth source with the assist of citric acid. By combining the results of X-ray powder diffraction, transmission electron microscope, scanning electron microscopy, and UV–Visible absorption spectra, the structural, morphological and optical properties characterization of the products were performed. The photocatalytic activity of the as-prepared α- and β-phase porous Bi2O3 microspheres have been tested by degradation of methylene orange under visible light, indicating that porous β-Bi2O3 microspheres showed enhanced photocatalytic performance compared to P25 and α-Bi2O3 microspheres.

The interaction and complex formation between cationic surfactants dimethyldioctadecylammonium Bromide (DODA-Br) and a polyoxomolybdate (POM)-based giant cluster {Mo72Fe30}, in its both single cluster (in aqueous solution, these clusters exist as anions) format and supramolecular format in aqueous solution, are studies by using laser light scattering (LLS) techniques. DODA/{Mo72Fe30} complexes containing basically single {Mo72Fe30} clusters are observed when the {Mo72Fe30} aqueous solution is freshly prepared and contains mainly unimer or oligmer {Mo72Fe30} anions. The {Mo72Fe30} clusters tend to form supramolecular vesicle structures slowly in solution. At high surfactant concentrations, the DODA cationic surfactants can break the vesicle structure and form single {Mo72Fe30}/DODA complexes. At low surfactant concentrations, complexes containing the whole vesicles coated by a layer of DODA is formed and transferred into the organic phase. For the surfactant concentrations in between, the vesicles are partially destroyed, leading to the formation of complexes with large size distribution. Studying the behaviors of the interaction between DODA and {Mo72Fe30} anionic structures will help to further explore the complicated mechanism of the POM vesicle formation, which was recently discovered but still not fully understood. Such unique complex structures may also have potential applications as nanoreactors or nanocontainers.

The emerging interest of ferrocenyl diphosphines in metal complexes has led to some significant developments recently in the clusters, polymetallic aggregates and oligomers of 1,1′-bis(diphenylphosphino)ferrocene (dppf). In this review, we shall focus on the synthetic strategies and the chemical, structural and bonding characteristics of these materials.