Direct evidence for ligand-enhanced activity of Cu(i) sites.

Little is known about the strong mediating effect of the ligand sphere and the coordination geometry on the strength and isotopologue selectivity of hydrogen adsorption on the undercoordinated copper(i) site. Here, we explore this effect using gas-phase complexes Cu(HO)(H) (with ≤ 3) as model systems. Cu(HO) attracts dihydrogen (82 kJ mol ) more strongly than bare Cu (64 kJ mol ) does.

Synthesis of Tridecacene by Multistep Single-Molecule Manipulation.

Acenes represent a unique class of polycyclic aromatic hydrocarbons that have fascinated chemists and physicists due to their exceptional potential for use in organic electronics. While recent advances in on-surface synthesis have resulted in higher acenes up to dodecacene, a comprehensive understanding of their fundamental properties necessitates their expansion toward even longer homologues. Here, we demonstrate the on-surface synthesis of tridecacene via atom-manipulation-induced conformational preparation and dissociation of a trietheno-bridged precursor on a Au(111) surface.

Decoding energy decomposition analysis: Machine-learned Insights on the impact of the density functional on the bonding analysis.

The concept of chemical bonding is a crucial aspect of chemistry that aids in understanding the complexity and reactivity of molecules and materials. However, the interpretation of chemical bonds can be hindered by the choice of the theoretical approach and the specific method utilized. This study aims to investigate the effect of choosing different density functionals on the interpretation of bonding achieved through energy decomposition analysis (EDA).

Binding Properties of Small Electrophilic Anions [B X ] and [B X ] (X=Cl, Br, I): Activation of Small Molecules Based on π-Backbonding.

Superelectrophilic anions constitute a special class of molecular anions that show strong binding of weak nucleophiles despite their negative charge. In this study, the binding characteristics of smaller gaseous electrophilic anions of the types [B X ] and [B X ] (with X=Cl, Br, I) were computationally and experimentally investigated and compared to those of the larger analogues [B X ] . The positive charge of vacant boron increases from [B X ] via [B X ] to [B X ] , as evidenced by increasing attachment enthalpies towards typical σ-donor molecules (noble gases, H O).

Machine learning for accelerated bandgap prediction in strain-engineered quaternary III-V semiconductors.

Quaternary III-V semiconductors are one of the most promising material classes in optoelectronics. The bandgap and its character, direct or indirect, are the most important fundamental properties determining the performance and characteristics of optoelectronic devices. Experimental approaches screening a large range of possible combinations of III- and V-elements with variations in composition and strain are impractical for every target application.

Visible-Light-Triggered Photoswitching of Diphosphene Complexes.

Although diphosphene transition metal complexes are known to undergo E to Z isomerization upon irradiation with UV light, their potential for photoswitching has remained poorly explored. In this study, we present diphosphene complexes capable of reversible photoisomerizations through haptotropic rearrangements. The compounds [(2-κ P,κ C)Mo(CO) ][OTf] (3 a[OTf]), [(2-κ P,κ C)Fe(CO)][OTf] (3 b[OTf]), and [(2-κ P)Fe(CO) ][OTf] (4[OTf]) were prepared using the triflate salt [(L )P=P(Dipp)][OTf] (2[OTf) as a precursor (L =4,5-dichloro-1,3-bis(2,6-diisiopropylphenyl)-imidazolin-2-yl; Dipp=2,6-diisiopropylphenyl, OTf=triflate).

Chemical bonding of HF, HCl, and H O onto YF surfaces: Quantification by first principles.

The surfaces of waimirite β- have been studied for their fluorine and chlorine versus water affinity. Bonding patterns of HF, HCl, and chemically adsorbed onto surfaces of (010), (100), (011), and (101) have been quantified by density functional theory applying energy decomposition analysis. We found that the adsorption of is dominated by about 65% of electrostatics, which causes a low surface sensitivity and weak interactions.

Synthesis of a rhodium(III) dinitrogen complex using a calix[4]arene-based diphosphine ligand.

The synthesis and characterisation of the rhodium(III) dinitrogen complex [Rh(2,2'-biphenyl)(CxP)(N)] are described, where CxP is a -spanning calix[4]arene-based diphosphine and the dinitrogen ligand is projected into the cavity of the macrocycle.

[SMe][BiAgI], a silver iodido bismuthate with an unusually small band gap.

Iodido metalates of heavy main group elements have seen much research interest in the last years due to their possible application as absorbers in photovoltaics. However, for materials based on the non-toxic element bismuth one challenge lies in narrowing the optical band gap for sufficient solar absorption. Here, we present a new iodido silver bismuthate, [SMe][BiAgI] (1), which is prepared from solution and characterized regarding its structure, thermal stability and optical absorption.

Topological Stone-Wales Defects Enhance Bonding and Electronic Coupling at the Graphene/Metal Interface.

Defects play a critical role for the functionality and performance of materials, but the understanding of the related effects is often lacking, because the typically low concentrations of defects make them difficult to study. A prominent case is the topological defects in two-dimensional materials such as graphene. The performance of graphene-based (opto-)electronic devices depends critically on the properties of the graphene/metal interfaces at the contacting electrodes.

Elucidating the Reaction Mechanism of Atomic Layer Deposition of AlO with a Series of Al(CH)Cl and Al(CH) Precursors.

The adsorption of metalorganic and metal halide precursors on the SiO surface plays an essential role in thin-film deposition processes such as atomic layer deposition (ALD). In the case of aluminum oxide (AlO) films, the growth characteristics are influenced by the precursor structure, which controls both chemical reactivity and the geometrical constraints during deposition. In this work, a systematic study using a series of Al(CH)Cl ( = 0, 1, 2, and 3) and Al(CH) ( = 1, 2, and 3) precursors is carried out using a combination of experimental spectroscopic techniques together with density functional theory calculations and Monte Carlo simulations to analyze differences across precursor molecules.

Bonding character of intermediates in on-surface Ullmann reactions revealed with energy decomposition analysis.

On-surface synthesis has become a thriving topic in surface science. The Ullmann coupling reaction is the most applied synthetic route today, but the nature of the organometallic intermediate is still under discussion. We investigate the bonding nature of prototypical intermediate species (phenyl, naphthyl, anthracenyl, phenanthryl, and triphenylenyl) on the Cu(111) surface with a combination of plane wave and atomic orbital basis set methods using density functional theory calculations with periodic boundary conditions.

Alkyne-Functionalized Cyclooctyne on Si(001): Reactivity Studies and Surface Bonding from an Energy Decomposition Analysis Perspective.

The reactivity and bonding of an ethinyl-functionalized cyclooctyne on Si(001) is studied by means of density functional theory. This system is promising for the organic functionalization of semiconductors. Singly bonded adsorption structures are obtained by [2 + 2] cycloaddition reactions of the cyclooctyne or ethinyl group with the Si(001) surface.