Revisiting ultrasmall phosphine-stabilized rhodium-doped gold clusters AunRh (n = 5, 6, 7, 8): geometric, electronic, and vibrational properties.

Incorporation of other transition metals in Au nanoclusters has been thriving recently due to its effect on their electronic and photophysical properties. Here, the ultrasmall phosphine-stabilized Rh-doped gold clusters AunRh (n = 5, 6, 7, 8), with metal core structures represented as fragments of a rhodium-centered icosahedron, are considered. The geometric and electronic properties of these nanoclusters are revisited and analyzed using density functional theory (DFT). Moreover, infrared spectra are simulated to identify the effects of Rh doping on the clusters through vibrational properties. Peaks are assigned to breathing-like normal modes for all AuRh clusters except for Au8Rh, likely due to the presence of bound Cl ligands. Unlike their pure gold core counterparts, the % motions of both Au and Rh atoms are lower in the mixed metal clusters, suggesting more restrained metal cores by rhodium, which could result in other novel physical and chemical properties not hitherto discovered.

Quantitative single-molecule study reveals site-specific photo-oxidation activities and kinetics on 2D g-C3N4.

We report the utilization of single-molecule fluorescence microscopy to in situ quantify the photo-oxidation reaction kinetics on g-C3N4. The wrinkle structure shows the highest reactivity and direct dissociation rate. The basal plane exhibits the highest affinity to reactants and products and indirect dissociation rate constant, followed by edges and wrinkles.

In situ quantitative single-molecule study of site-specific photocatalytic activity and dynamics on ultrathin g-C3N4 nanosheets.

Graphitic carbon nitride (g-C3N4) has attracted extensive research attention in recent years due to its unique layered structure, facile synthetic route, visible-light-responsive nature, and excellent photocatalytic performance. However, an insightful investigation of site-specific catalytic activities and kinetics on g-C3N4 is still warranted. Here, we fabricated ultrathin g-C3N4 nanosheets through thermal exfoliation. The optimized sample exhibits a high specific surface area of 307.35 m2 g-1 and a remarkable H2 generation activity of 2008 µmol h-1 g-1 with an apparent quantum efficiency of 4.62% at λ = 420 nm. Single-molecule fluorescence microscopy was applied for the first time to spatially resolve the reaction heterogeneities with nanometer precision (∼10 nm). The catalytic kinetics (i.e., reactant adsorption, conversion, and product dissociation) and temporal activity fluctuations were in situ quantified at individual structural features (i.e., wrinkles, edges, and basal planes) of g-C3N4. It was found that the wrinkle and edge exhibited superior photocatalytic activity due to the intrinsic band modulation, which are 20 times and 14.8 times that of the basal plane, respectively. Moreover, due to the steric effect, the basal plane showed the highest adsorption constant and the lowest direct dissociation constant. Density functional theory (DFT) simulations unveiled the adsorption energies of reactant and product molecules on each structure of g-C3N4, which support our experimental results. Such investigation would shed more light on the fundamental understanding of site-specific catalytic dynamics on g-C3N4, which benefits the rational design of 2D layered materials for efficient solar-to-chemical energy conversion.

A Review of State of the Art in Phosphine Ligated Gold Clusters and Application in Catalysis.

Atomically precise gold clusters are highly desirable due to their well-defined structure which allows the study of structure-property relationships. In addition, they have potential in technological applications such as nanoscale catalysis. The structural, chemical, electronic, and optical properties of ligated gold clusters are strongly defined by the metal-ligand interaction and type of ligands. This critical feature renders gold-phosphine clusters unique and distinct from other ligand-protected gold clusters. The use of multidentate phosphines enables preparation of varying core sizes and exotic structures beyond regular polyhedrons. Weak gold-phosphorous (Au-P) bonding is advantageous for ligand exchange and removal for specific applications, such as catalysis, without agglomeration. The aim of this review is to provide a unified view of gold-phosphine clusters and to present an in-depth discussion on recent advances and key developments for these clusters. This review features the unique chemistry, structural, electronic, and optical properties of gold-phosphine clusters. Advanced characterization techniques, including synchrotron-based spectroscopy, have unraveled substantial effects of Au-P interaction on the composition-, structure-, and size-dependent properties. State-of-the-art theoretical calculations that reveal insights into experimental findings are also discussed. Finally, a discussion of the application of gold-phosphine clusters in catalysis is presented.

Self-sorting of porous Cu4L2L'2 metal-organic cages composed of isomerisable ligands.

We report the self-sorting of a dynamic combinatorial library (DCL) of metal-organic cages composed of a rotationally isomerisable ligand. Convergence of the DCL occurs upon crystallisation and leads to low-symmetry Cu4L2L'2 cages that display differing porosities based on their overall shape and ligand configuration.

Density-functional tight-binding for phosphine-stabilized nanoscale gold clusters.

We report a parameterization of the second-order density-functional tight-binding (DFTB2) method for the quantum chemical simulation of phosphine-ligated nanoscale gold clusters, metalloids, and gold surfaces. Our parameterization extends the previously released DFTB2 "auorg" parameter set by connecting it to the electronic parameter of phosphorus in the "mio" parameter set. Although this connection could technically simply be accomplished by creating only the required additional Au-P repulsive potential, we found that the Au 6p and P 3d virtual atomic orbital energy levels exert a strong influence on the overall performance of the combined parameter set. Our optimized parameters are validated against density functional theory (DFT) geometries, ligand binding and cluster isomerization energies, ligand dissociation potential energy curves, and molecular orbital energies for relevant phosphine-ligated Au n clusters (n = 2-70), as well as selected experimental X-ray structures from the Cambridge Structural Database. In addition, we validate DFTB simulated far-IR spectra for several phosphine- and thiolate-ligated gold clusters against experimental and DFT spectra. The transferability of the parameter set is evaluated using DFT and DFTB potential energy surfaces resulting from the chemisorption of a PH3 molecule on the gold (111) surface. To demonstrate the potential of the DFTB method for quantum chemical simulations of metalloid gold clusters that are challenging for traditional DFT calculations, we report the predicted molecular geometry, electronic structure, ligand binding energy, and IR spectrum of Au108S24(PPh3)16.

Anisotropic and amphoteric characteristics of diverse carbenes.

Despite its key importance in carbene chemistry, the amphoteric (i.e., both nucleophilic and electrophilic) behavior of the divalent carbon atom (:C) in carbenes is not well understood. The electrostatic potential (EP) around :C is often incorrectly described by simple isotropic atomic charges (particularly, as in singlet CF2); therefore, it should be described by the multipole model, which can illustrate both negative and positive EPs, favoring the positively and negatively charged species that are often present around :C. This amphotericity is much stronger in the singlet state, which has more conspicuous anisotropic charge distribution than the triplet state; this is validated by the complexation structures of carbenes interacting with Na+, Cl-, H2O, and Ag+. From the study of diverse carbenes [including CH2, CLi2/CNa2, CBe2/CMg2, CF2/CCl2, C(BH2)2/C(AlH2)2, C(CH3)2/C(SiH3)2, C(NH2)2/C(PH2)2, cyclic systems of C(CH2)2/C(CH)2, C(BHCH)2, C(CH2CH)2/C(CHCH)2, and C(NHCH)2/C(NCH)2], we elucidate the relationships between the electron configurations, electron accepting/donating strengths of atoms attached to :C, π conjugation, singlet-triplet energy gaps, anisotropic hard wall radii, anisotropic electrostatic potentials, and amphotericities of carbenes, which are vital to carbene chemistry. The (σ2, π2 or σπ) electronic configuration associated with :C on the :CA2 plane (where A is an adjacent atom) in singlet and triplet carbenes largely governs the amphoteric behaviors along the :C tip and :C face-on directions. The :C tip and :C face-on sites of σ2 singlet carbenes tend to show negative and positive EPs, favoring nucleophiles and electrophiles, respectively; meanwhile, those of π2 singlet carbenes, such as very highly π-conjugated 5-membered cyclic C(NCH)2, tend to show the opposite behavior. Open-shell σπ singlet (such as highly π-conjugated 5-membered cyclic C(CHCH)2) and triplet carbenes show less anisotropic and amphoteric behaviors.

Size-dependent conformational change in halogen-π interaction: from benzene to graphene.

Diatomic halogen molecules X2 (X = Cl/Br) favor the edge-to-face conformation on benzene with significant electrostatic interaction via halogen bonding. In contrast, they favor the stacked conformation on graphene with negligible electrostatic interaction. As the aromatic ring expands, the inner facial side becomes almost electrostatically neutral. On coronene, the two conformations are compatible.

Halogen-π Interactions between Benzene and X2/CX4 (X = Cl, Br): Assessment of Various Density Functionals with Respect to CCSD(T).

Various types of interactions between halogen (X) and π moiety (X-π interaction) including halogen bonding play important roles in forming the structures of biological, supramolecular, and nanomaterial systems containing halogens and aromatic rings. Furthermore, halogen molecules such as X2 and CX4 (X = Cl/Br) can be intercalated in graphite and bilayer graphene for doping and graphene functionalization/modification. Due to the X-π interactions, though recently highly studied, their structures are still hardly predictable. Here, using the coupled-cluster with single, double, and noniterative triple excitations (CCSD(T)), the Møller-Plesset second-order perturbation theory (MP2), and various flavors of density functional theory (DFT) methods, we study complexes of benzene (Bz) with halogen-containing molecules X2 and CX4 (X = Cl/Br) and analyze various components of the interaction energy using symmetry adapted perturbation theory (SAPT). As for the lowest energy conformers (S1), X2-Bz is found to have the T-shaped structure where the electropositive X atom-end of X2 is pointing to the electronegative midpoint of CC bond of the Bz ring, and CX4-Bz has the stacked structure. In addition to this CX4-Bz (S1), other low energy conformers of X2-Bz (S2/S3) and CX4-Bz (S2) are stabilized primarily by the dispersion interaction, whereas the electrostatic interaction is substantial. Most of the density functionals show noticeable deviations from the CCSD(T) complete basis set (CBS) limit binding energies, especially in the case of strongly halogen-bonded conformers of X2-Bz (S1), whereas the deviations are relatively small for CX4-Bz where the dispersion is more important. The halogen bond shows highly anisotropic electron density around halogen atoms and the DFT results are very sensitive to basis set. The unsatisfactory performance of many density functionals could be mainly due to less accurate exchange. This is evidenced from the good performance by the dispersion corrected hybrid and double hybrid functionals. B2GP-PLYP-D3 and PBE0-TS(Tkatchenko-Scheffler)/D3 are well suited to describe the X-π interactions adequately, close to the CCSD(T)/CBS binding energies (within ∼1 kJ/mol). This understanding would be useful to study diverse X-π interaction driven structures such as halogen containing compounds intercalated between 2-dimensional layers.

Intriguing Electrostatic Potential of CO: Negative Bond-ends and Positive Bond-cylindrical-surface.

The strong electronegativity of O dictates that the ground state of singlet CO has positively charged C and negatively charged O, in agreement with ab initio charge analysis, but in disagreement with the dipole direction. Though this unusual phenomenon has been fairly studied, the study of electrostatic potential (EP) for noncovalent interactions of CO is essential for better understanding. Here we illustrate that both C and O atom-ends show negative EP (where the C end gives more negative EP), favoring positively charged species, whereas the cylindrical surface of the CO bond shows positive EP, favoring negatively charged ones. This is demonstrated from the interactions of CO with Na(+), Cl(-), H2O, CO and benzene. It can be explained by the quadrupole driven electrostatic nature of CO (like N2) with very weak dipole moment. The EP is properly described by the tripole model taking into account the electrostatic multipole moments, which has a large negative charge at a certain distance protruded from C, a large positive charge on C, and a small negative charge on O. We also discuss the EP of the first excited triplet CO.