Understanding the 1,3-Dipolar Cycloadditions of Allenes.

We have quantum chemically studied the reactivity, site-, and regioselectivity of the 1,3-dipolar cycloaddition between methyl azide and various allenes, including the archetypal allene propadiene, heteroallenes, and cyclic allenes, by using density functional theory (DFT). The 1,3-dipolar cycloaddition reactivity of linear (hetero)allenes decreases as the number of heteroatoms in the allene increases, and formation of the 1,5-adduct is, in all cases, favored over the 1,4-adduct. Both effects find their origin in the strength of the primary orbital interactions.

Dataset of the application of handheld NIR and machine learning for chicken fillet authenticity study.

Diffuse reflectance near-infrared (NIR) data (908-1676 nm) of chicken breast fillets was recorded in a non-destructive way using a portable miniaturised NIR spectrometer. The NIR data was used to discriminate between fresh and thawed breast fillets and to determine the birds' growth conditions. NIR data was recorded of 153 commercial supermarket chicken fillet samples by applying the NIR device equipped with the standard issue collar on the samples in three different ways: (i) directly on the meat (ii) through the top foil of the package (i.

Ambident Nucleophilic Substitution: Understanding Non-HSAB Behavior through Activation Strain and Conceptual DFT Analyses.

The ability to understand and predict ambident reactivity is key to the rational design of organic syntheses. An approach to understand trends in ambident reactivity is the hard and soft acids and bases (HSAB) principle. The recent controversy over the general validity of this principle prompted us to investigate the competing gas-phase S 2 reaction channels of archetypal ambident nucleophiles CN , OCN , and SCN with CH Cl (S 2@C) and SiH Cl (S 2@Si), using DFT calculations.

How Lewis Acids Catalyze Diels-Alder Reactions.

The Lewis acid(LA)-catalyzed Diels-Alder reaction between isoprene and methyl acrylate was investigated quantum chemically using a combined density functional theory and coupled-cluster theory approach. Computed activation energies systematically decrease as the strength of the LA increases along the series I View Article and Find Full Text PDF

Ligand-Mediated Regioselective Rhodium-Catalyzed Benzotriazole-Allene Coupling: Mechanistic Exploration and Quantum Chemical Analysis.

The ligand-controlled rhodium-catalyzed regioselective coupling of 1,2,3-benzotriazoles and allenes was investigated by DFT calculations. Because allylation can occur at either the N1 or N2 position of the 1,2,3-benzotriazole, the complete Gibbs free energy profiles for both pathways were computed. A kinetic preference emerged for the experimentally observed N1 allylation with the JoSPOphos ligand, whereas N2 allylation was favored with DPEphos.

Toward Transition-Metal-Templated Construction of Arylated B Chains by Dihydroborane Dehydrocoupling.

The reactivity of a diruthenium tetrahydride complex towards three selected dihydroboranes was investigated. The use of [DurBH ] (Dur=2,3,5,6-Me C H) and [(Me Si) NBH ] led to the formation of bridging borylene complexes of the form [(Cp*RuH) BR] (Cp*=C Me ; 1 a: R=Dur; 1 b: R=N(SiMe ) ) through oxidative addition of the B-H bonds with concomitant hydrogen liberation. Employing the more electron-deficient dihydroborane [3,5-(CF ) -C H BH ] led to the formation of an anionic complex bearing a tetraarylated chain of four boron atoms, namely Li(THF) [(Cp*Ru) B H (3,5-(CF ) C H ) ] (4), through an unusual, incomplete threefold dehydrocoupling process.

Robust thermoelastic microactuator based on an organic molecular crystal.

Mechanically responsive molecular crystals that reversibly change shape triggered by external stimuli are invaluable for the design of actuators for soft robotics, artificial muscles and microfluidic devices. However, their strong deformations usually lead to their destruction. We report a fluorenone derivative (4-DBpFO) showing a strong shear deformation upon heating due to a structural phase transition which is reproducible after more than hundred heating/cooling cycles.

Steric Effects Dictate the Formation of Terminal Arylborylene Complexes of Ruthenium from Dihydroboranes.

The steric and electronic properties of aryl substituents in monoaryl borohydrides (Li[ArBH ]) and dihydroboranes were systematically varied and their reactions with [Ru(PCy ) HCl(H )] (Cy: cyclohexyl) were studied, resulting in bis(σ)-borane or terminal borylene complexes of ruthenium. These variations allowed for the investigation of the factors involved in the activation of dihydroboranes in the synthesis of terminal borylene complexes. The complexes were studied by multinuclear NMR spectroscopy, mass spectrometry, X-ray diffraction analysis, and density functional theory (DFT) calculations.

Dual Activation of Aromatic Diels-Alder Reactions.

The unusually fast Diels-Alder reactions of [5]cyclophanes were analyzed by DFT at the BLYP-D3(BJ)/TZ2P level of theory. The computations were guided by an integrated activation-strain and Kohn-Sham molecular orbital analysis. It is revealed why both [5]metacyclophane and [5]paracyclophane exhibit a significant rate enhancement compared to their planar benzene analogue.

How Dihalogens Catalyze Michael Addition Reactions.

We have quantum chemically analyzed the catalytic effect of dihalogen molecules (X =F , Cl , Br , and I ) on the aza-Michael addition of pyrrolidine and methyl acrylate using relativistic density functional theory and coupled-cluster theory. Our state-of-the-art computations reveal that activation barriers systematically decrease as one goes to heavier dihalogens, from 9.4 kcal mol for F to 5.

Halide Perovskites for Nonlinear Optics.

Halide perovskites provide an ideal platform for engineering highly promising semiconductor materials for a wide range of applications in optoelectronic devices, such as photovoltaics, light-emitting diodes, photodetectors, and lasers. More recently, increasing research efforts have been directed toward the nonlinear optical properties of halide perovskites because of their unique chemical and electronic properties, which are of crucial importance for advancing their applications in next-generation photonic devices. Here, the current state of the art in the field of nonlinear optics (NLO) in halide perovskite materials is reviewed.

ssNake: A cross-platform open-source NMR data processing and fitting application.

For solid-state NMR or for unconventional experiments only a very limited number of modern processing and simulation software packages are available. For this reason, we have developed ssNake, an NMR processing program which provides both interactive and script-based processing tools. ssNake is aimed at solid-state NMR experiments, but can also be used for liquid-state experiments.

Structural Distortion of Cycloalkynes Influences Cycloaddition Rates both by Strain and Interaction Energies.

The reactivities of 2-butyne, cycloheptyne, cyclooctyne, and cyclononyne in the 1,3-dipolar cycloaddition reaction with methyl azide were evaluated through DFT calculations at the M06-2X/6-311++G(d)//M06-2X/6-31+G(d) level of theory. Computed activation free energies for the cycloadditions of cycloalkynes are 16.5-22.

Half-Sandwich Metal-Catalyzed Alkyne [2+2+2] Cycloadditions and the Slippage Span Model.

Half-sandwich Rh compounds display good catalytic activity toward alkyne [2+2+2] cycloadditions. A peculiar structural feature of these catalysts is the coordination of the metal to an aromatic moiety, typically a cyclopentadienyl anion, and, in particular, the possibility to change the bonding mode easily by the metal slipping over this aromatic moiety. Upon modifying the ancillary ligands, or proceeding along the catalytic cycle, hapticity changes can be observed; it varies from η, if the five metal-carbon distances are identical, through η+η, in the presence of allylic distortion, and η, in the case of allylic coordination, to η, if a σ metal-carbon bond forms.

Critical comparison of methods for fault diagnosis in metabolomics data.

Platforms like metabolomics provide an unprecedented view on the chemical versatility in biomedical samples. Many diseases reflect themselves as perturbations in specific metabolite combinations. Multivariate analyses are essential to detect such combinations and associate them to specific diseases.

Satellite nutation of half integer quadrupolar nuclei: Theory and practice.

For quadrupolar spin systems, interpretation of solid state NMR spectra can be hampered by the presence of resonances from both satellite and central transitions. This is particularly true for disordered systems, where many different quadrupolar sites exist, which can have strongly different quadrupolar coupling constants. If second order effects are too strong for obtaining meaningful MAS, MQMAS or STMAS spectra, an approach is needed to successfully separate central and satellite transitions.

Enhanced Second Harmonic Generation from Ferroelectric HfO-Based Hybrid Metasurfaces.

Integrated nonlinear metasurfaces leading to high-efficiency optical second harmonic generation (SHG) are highly desirable for optical sensing, imaging, and quantum photonic systems. Compared to traditional metal-only metasurfaces, their hybrid counterparts, where a noncentrosymmetric nonlinear photonic material is incorporated in the near-field of a metasurface, can significantly boost SHG efficiency. However, it is difficult to integrate such devices on-chip due to material incompatibilities, thickness scaling challenges, and the narrow band gaps of nonlinear optical materials.

Diels-Alder reactivities of cycloalkenediones with tetrazine.

Quantum chemical calculations were used to investigate the Diels-Alder reactivities for a series of cycloalkenediones with tetrazine. We find that the reactivity trend of cycloalkenediones toward tetrazine is opposite to cycloalkenes. The electrostatic interactions between the cycloalkenediones and tetrazine become more stabilizing as the ring size of the cycloalkenediones increases, resulting in lower activation energies.

Angle Distribution of Loading Subspace (ADLS) for estimating chemical rank in multivariate analysis: Applications in spectroscopy and chromatography.

Multivariate analyses are increasingly popular to explore the underlying structure of multivariate datasets, which are more and more prevalent in analytical chemistry. However, difficulties can be associated with estimating the number of components for the data with considerable coherence and noise. The method of Angle Distribution of Loading Subspace (ADLS) has been proposed to estimate the number of components for Principal Component Analysis (PCA) and PARAllel FACtor analysis (PARAFAC), which showed some advantages, in particular in the case of datasets with high coherence, over the commonly used methods (scree plot and cross-validation in PCA, and core consistency diagnostics (CORCONDIA) in PARAFAC).

Factors Controlling the Diels-Alder Reactivity of Hetero-1,3-Butadienes.

We have quantum chemically explored the Diels-Alder reactivities of a systematic series of hetero-1,3-butadienes with ethylene by using density functional theory at the BP86/TZ2P level. Activation strain analyses provided physical insight into the factors controlling the relative cycloaddition reactivity of aza- and oxa-1,3-butadienes. We find that dienes with a terminal heteroatom, such as 2-propen-1-imine ( or acrolein (, are less reactive than the archetypal 1,3-butadiene (), primarily owing to weaker orbital interactions between the more electronegative heteroatoms with ethylene.

Author Correction: Non-collinear spin states in bottom-up fabricated atomic chains.

The original version of this Article contained an error in Fig. 3 in which Fig. 3b and Fig.

Chemoselectivity of Tertiary Azides in Strain-Promoted Alkyne-Azide Cycloadditions.

The strain-promoted alkyne-azide cycloaddition (SPAAC) is the most commonly employed bioorthogonal reaction with applications in a broad range of fields. Over the years, several different cyclooctyne derivatives have been developed and investigated in regard to their reactivity in SPAAC reactions with azides. However, only a few studies examined the influence of structurally diverse azides on reaction kinetics.

Chiral Lead Halide Perovskite Nanowires for Second-Order Nonlinear Optics.

Hybrid organic/inorganic lead halide perovskites (LHPs) have recently emerged as extremely promising photonic materials. However, the exploration of their optical nonlinearities has been mainly focused on the third- and higher-order nonlinear optical (NLO) effects. Strong second-order NLO responses are hardly expected from ordinary LHPs due to their intrinsic centrosymmetric structures, but are highly desirable for advancing their applications in the next generation integrated photonic circuits.

Hyphenation of Supercritical Fluid Chromatography and NMR with In-Line Sample Concentration.

By coupling supercritical fluid chromatography (SFC) and nuclear magnetic resonance (NMR) in-line, a powerful analytical method arises that enables chemically specific analysis of a broad range of complex mixtures. However, during chromatography, the compounds are diluted in the mobile phase, in this case supercritical CO (scCO), often resulting in concentrations that are too low to be detected by NMR spectroscopy or at least requiring excessive signal averaging. We present a hyphenated SFC-NMR setup with an integrated approach for concentrating samples in-line, which are diluted in scCO during chromatography.

Non-collinear spin states in bottom-up fabricated atomic chains.

Non-collinear spin states with unique rotational sense, such as chiral spin-spirals, are recently heavily investigated because of advantages for future applications in spintronics and information technology and as potential hosts for Majorana Fermions when coupled to a superconductor. Tuning the properties of such spin states, e.g.