Single-Molecule Magnets DyM2N@C80 and Dy2MN@C80 (M=Sc,Lu): The Impact of Diamagnetic Metals on Dy3+ Magnetic Anisotropy,Dy⋅⋅⋅Dy Coupling,and Mixing of Molecular and Lattice Vibrations

The substitution of scandium in fullerene single-molecule magnets (SMMs) DySc₂N@C₈₀ and Dy₂ScN@C₈₀ by lutetium has been studied to explore the influence of the diamagnetic metal on the SMM performance of dysprosium nitride clusterfullerenes. The use of lutetium led to an improved SMM performance of DyLu₂N@C₈₀, which shows a higher blocking temperature of magnetization (T_B=9.5 K), longer relaxation times, and broader hysteresis than DySc₂N@C₈₀ (T_B=6.9 K). At the same time, Dy₂LuN@C₈₀ was found to have a similar blocking temperature of magnetization to Dy₂ScN@C₈₀ (T_B=8 K), but substantially different interactions between the magnetic moments of the dysprosium ions in the Dy₂MN clusters. Surprisingly, although the intramolecular dipolar interactions in Dy₂LuN@C₈₀ and Dy₂ScN@C₈₀ are of similar strength, the exchange interactions in Dy₂LuN@C₈₀ are close to zero. Analysis of the low-frequency molecular and lattice vibrations showed strong mixing of the lattice modes and endohedral cluster librations in k-space. This mixing simplifies the spin–lattice relaxation by conserving the momentum during the spin flip and helping to distribute the moment and energy further into the lattice.     

Evaluation of Pd→B Interactions in Diphosphinoborane Complexes and Impact on Inner-Sphere Reductive Elimination

The dative Pd→B interaction in a series of ^RDPB^R’ Pd⁰ and Pd^II complexes (^RDPB^R’=(o-PR₂C₆H₄)₂BR’, diphosphinoborane) was analyzed using XRD, ¹¹B NMR spectroscopy and NBO/NLMO calculations. The borane acceptor discriminates between the oxidation state Pd^II and Pd⁰, stabilizing the latter. Reaction of lithium amides with [(^RDPB^R’)Pd^II(4-NO₂C₆H₄)I] chemoselectively yields the C−N coupling product. DFT modelling indicates no significant impact of Pd^II→B coordination on the inner-sphere reductive elimination rate.     

On‐Surface Assembly of Hydrogen‐ and Halogen‐Bonded Supramolecular Graphyne‐Like Networks

Demonstrated here is a supramolecular approach to fabricate highly ordered monolayered hydrogen‐ and halogen‐bonded graphyne‐like two‐dimensional (2D) materials from triethynyltriazine derivatives on Au(111) and Ag(111). The 2D networks are stabilized by N???H?C(sp) bonds and N???Br?C(sp) bonds to the triazine core. The structural properties and the binding energies of the supramolecular graphynes have been investigated by scanning tunneling microscopy in combination with density‐functional theory calculations. It is revealed that the N???Br?C(sp) bonds lead to significantly stronger bonded networks compared to the hydrogen‐bonded networks. A systematic analysis of the binding energies of triethynyltriazine and triethynylbenzene derivatives further demonstrates that the X₃‐synthon, which is commonly observed for bromobenzene derivatives, is weaker than the X₆‐synthon for our bromotriethynyl derivatives.     

Atom Exchange Versus Reconstruction: (GexAs4−x)x− (x=2, 3) as Building Blocks for the Supertetrahedral Zintl Cluster [Au6(Ge3As)(Ge2As2)3]3−

The Zintl anion (Ge₂As₂)^2? represents an isostructural and isoelectronic binary counterpart of yellow arsenic, yet without being studied with the same intensity so far. Upon introducing [(PPh₃)AuMe] into the 1,2‐diaminoethane (en) solution of (Ge₂As₂)^2?, the heterometallic cluster anion [Au₆(Ge₃As)(Ge₂As₂)₃]^3? is obtained as its salt [K(crypt‐222)]₃[Au₆(Ge₃As)(Ge₂As₂)₃]?en?2 tol ( 1 ). The anion represents a rare example of a superpolyhedral Zintl cluster, and it comprises the largest number of Au atoms relative to main group (semi)metal atoms in such clusters. The overall supertetrahedral structure is based on a (non‐bonding) octahedron of six Au atoms that is face‐capped by four (Ge_xAs_4?x)^x? (x=2, 3) units. The Au atoms bind to four main group atoms in a rectangular manner, and this way hold the four units together to form this unprecedented architecture. The presence of one (Ge₃As)^3? unit besides three (Ge₂As₂)^2? units as a consequence of an exchange reaction in solution was verified by detailed quantum chemical (DFT) calculations, which ruled out all other compositions besides [Au₆(Ge₃As)(Ge₂As₂)₃]^3?. Reactions of the heavier homologues (Tt₂Pn₂)^2? (Tt=Sn, Pb; Pn=Sb, Bi) did not yield clusters corresponding to that in 1 , but dimers of ternary nine‐vertex clusters, {[AuTt₅Pn₃]₂}^4? (in 2 – 4 ; Tt/Pn=Sn/Sb, Sn/Bi, Pb/Sb), since the underlying pseudo‐tetrahedral units comprising heavier atoms do not tend to undergo the said exchange reactions as readily as (Ge₂As₂)^2?, according to the DFT calculations.     

Asymmetric Hydroformylation Using a Rhodium Catalyst Encapsulated in a Chiral Capsule

Supramolecular capsules can be used to change the activity and selectivity of a catalyst through the influence of the second coordination sphere, reminiscent of how enzymes control the selectivity of their processes. In enzymes, this approach is used to also control the enantioselectivity of reactions in which the active catalytic site is often not chiral but the second coordination sphere is. We are interested in the possibility to generate a chiral second coordination sphere around an otherwise achiral transition metal complex for asymmetric catalysis. In this paper we show that the ligand template approach can be used to generate a chiral second coordination sphere around a rhodium complex, which is used in asymmetric hydroformylation.     

Synthesis of Structurally Complex Silicon Frameworks through the First Sila-Aldol Reaction

Herein, we report on the first sila-aldol reaction, which emphasizes the tight connection between silicon and carbon chemistry. This novel synthetic method provides straightforward access to 2-oxahexasilabicyclo[3.2.1]octan-8-ide, a structurally complex silicon framework, in quantitative yield. Its structure was confirmed by NMR spectroscopy and X-ray crystallography, and it displays a distinctive charge-transfer transition. The complete mechanism of this highly selective rearrangement cascade is outlined and supported by density functional theory (DFT) calculations, which highlight the thermodynamic driving force and the low activation barriers of this powerful silicon–carbon bond-forming strategy.     

Highly Stable,Low Gas Crossover,Proton-Conducting Phenylated Polyphenylenes

Two classes of novel sulfonated phenylated polyphenylene ionomers are investigated as polyaromatic-based proton exchange membranes. Both types of ionomer possess high ion exchange capacities yet are insoluble in water at elevated temperatures. They exhibit high proton conductivity under both fully hydrated conditions and reduced relative humidity, and are markedly resilient to free radical attack. Fuel cells constructed with membrane-electrode assemblies containing each ionomer membrane yield high in situ proton conductivity and peak power densities that are greater than obtained using Nafion reference membranes. In situ chemical stability accelerated stress tests reveal that this class of the polyaromatic membranes allow significantly lower gas crossover and lower rates of degradation than Nafion benchmark systems. These results point to a promising future for molecularly designed sulfonated phenylated polyphenylenes as proton-conducting media in electrochemical technologies.     

Quantification of Noncovalent Interactions in Azide–Pnictogen, –Chalcogen,and –Halogen Contacts

The noncovalent interactions between azides and oxygen-containing moieties are investigated through a computational study based on experimental findings. The targeted synthesis of organic compounds with close intramolecular azide–oxygen contacts yielded six new representatives, for which X-ray structures were determined. Two of those compounds were investigated with respect to their potential conformations in the gas phase and a possible significantly shorter azide–oxygen contact. Furthermore, a set of 44 high-quality, gas-phase computational model systems with intermolecular azide–pnictogen (N, P, As, Sb), –chalcogen (O, S, Se, Te), and –halogen (F, Cl, Br, I) contacts are compiled and investigated through semiempirical quantum mechanical methods, density functional approximations, and wave function theory. A local energy decomposition (LED) analysis is applied to study the nature of the noncovalent interaction. The special role of electrostatic and London dispersion interactions is discussed in detail. London dispersion is identified as a dominant factor of the azide–donor interaction with mean London dispersion energy-interaction energy ratios of 1.3. Electrostatic contributions enhance the azide–donor coordination motif. The association energies range from −1.00 to −5.5 kcal mol⁻¹.