Direct synthesis of hyperbranched ethene oligomers and ethene-MA co-oligomers using iminopyridyl systems with weak neighboring group interactions

The synthesis of hyper-branched ethene oligomers through catalytic insertion reactions with late transition metal catalysts is unique in its synthetic and practical scope. In this study, a series of iminopyridyl Ni(II) and Pd(II) complexes with electron-rich distal aryl motifs were synthesized and characterized. These complexes were very efficient in ethene oligomerization and co-oligomerization with methyl acrylate (MA). Hyperbranched ethene oligomers with different microstructures were generated using different metal species in ethene oligomerization. More importantly, hyperbranched ethene-MA co-oligomers with varying incorporation ratios were generated via ethene and MA co-oligomerization using the Pd(II) complexes. Most notably, weak neighboring group interactions of distal aryl motifs in the nickel system are more effective in influencing the microstructure of ethene oligomers than the corresponding palladium system.     

Macroscopic Polarization Change of Mononuclear Valence Tautomeric Cobalt Complexes Through the Use of Enantiopure Ligand

The crystallization of a complex having electron transfer properties in a polar space group can induce the polarization switching of a crystal in a specific direction, which is attractive for the development of sensors, memory devices, and capacitors. Unfortunately, the probability of crystallization in a polar space group is usually low. Noticing that enantiopure compounds crystallize in Sohncke space groups, this paper reports a strategy for the molecular design of non-ferroelectric polarization switching crystals based on the use of intramolecular electron transfer and chirality. In addition, this paper describes the synthesis of a mononuclear valence tautomeric (VT) cobalt complex bearing an enantiopure ligand. The introduction of enantiomer enables the crystallization of the complex in the polar space group (P2₁). The polarization of the crystals along the b-axis direction is not canceled out and the VT transition is accompanied by a change in the macroscopic polarization of the polar crystal. Polarization switching via electron transfer is realized at around room temperature.     

Electronic and optical properties of quaternary selenides for optoelectronic applications: Insights from DFT+U-computations

The optical properties, electronic charge density, electronic structure of the new layered selenides materials, BaGdCuSe₃, CsUCuSe₃, CsZrCuSe₃, and CsGdZnSe₃ compounds have been calculated by using the full potential and linear augmented plane wave (FP-LAPW) methods as applied in the WIEN2k package, which is based on the density functional theory. The ALnMSe3 compound's structure of these was (A = Cs, Ba; Ln = Zr, Gd, U; M = Cu, Zn) is composed of (n = 1, 2) layers, which might be separated by A atoms. It is to be observed that there is strong hybridization between the s, p, and d states of Zr, Gd, and Cu atoms. Around the gadolinium atom, the charge density contours are completely circular, but the Gadolinium “Gd” atom shows an ionic nature. To calculate the refractive index, we used Kramer's Kronig correlations with the imaginary part dielectric function. The decrease in the refractive index is due to the lack of probability for direct excitation of the electrons, resulting in a loss of energy. The value of the static refractive index for all reference compounds is about 1.75–2.25, which is indication that the material used in optoelectronic devices.     

Bonding situations in tricoordinated beryllium phenyl complexes

The bonding situation in the tricoordinated beryllium phenyl complexes [BePh₃]⁻, [(pyridine)BePh₂] and [(trimethylsilyl-N-heterocyclic imine)BePh₂] is investigated experimentally and computationally. Comparison of the NMR spectroscopic properties of these complexes and of their structural parameters, which were determined by single crystal X-ray diffraction experiments, indicates the presence of π-interactions. Topology analysis of the electron density reveals elliptical electron density distributions at the bond critical points and the double bond character of the beryllium-element bonds is verified by energy decomposition analysis with the combination of natural orbital for chemical valence. The present beryllium-element bonds are highly polarized and the ligands around the central atom have a strong influence on the degree of π-delocalization. These results are compared to related triarylboranes.     

Lewis acid stabilized group 13–15 element analogs of ethylene

Stabilization of hydrogen-substituted group 13–15 compounds H₂EE′H₂ (E = B, Al, Ga; E′ = P, As, Sb) by Lewis acids is considered at B3LYP/def2-TZVP, B3LYP-D3/def2-TZVP and M06-2X/def2-TZVP levels of theory. It is shown, that for many Lewis acids additional reactivity beyond the DA complex formation with H₂EE′H₂ monomer is expected. In case of complexation with E(C₆F₅)₃, F/H exchange reactions with group 13 bound hydrides are predicted to be exothermic and accompanied by the activation energies which are smaller than dissociation of the complex into components. In case of complex formation with transition metal (TM) carbonyls, additional O → Al, TM–C → Al interactions are observed, which in several cases lead to cyclic structures. The most promising candidates for the experimental studies have been identified. Synthetic approaches to the most promising LA-only stabilized compounds are recommended.     

Radical-Bridged Heterometallic Single-Molecule Magnets Incorporating Four Lanthanoceniums

The syntheses and magnetic properties of organometallic heterometallic compounds [K(THF)₆]{Co^I[(μ₃-HAN)RE₂Cp*₄]₂} ( 1-RE ) and [K(Crypt)]₂{Co^I[(μ₃-HAN)RE₂Cp*₄]₂} ( 2-RE ) containing hexaazatrinaphthylene radicals (HAN⋅³⁻) and four rare earth (RE) ions are reported. 1-RE shows isolable species with ligand-based mixed valency as revealed by cyclic voltammetry (CV) thus leading to the isolation of 2-RE via one-electron chemical reduction. Strong electronic communication in mixed-valency supports stronger overall ferromagnetic behaviors in 2-RE than 1-RE containing Gd and Dy ions. Ac magnetic susceptibility data reveal 1-Dy and 2-Dy both exhibit slow magnetic relaxation. Importantly, larger coercive field was observed in the hysteresis of 2-Dy at 2.0 K, indicating the enhanced SMM behavior compared with 1-Dy . Ligand-based mixed-valency strategy has been used for the first time to improve the magnetic coupling in lanthanide (Ln) SMMs, thus opening up new ways to construct strongly coupled Ln-SMMs.     

A Fujiwara-Moritani-Type Alkenylation Using a Traceless Directing Group Strategy: A Rare Example of C−C Bond Formation towards the C2-Carbon of Terminal Alkenes

Herein we report, a rhodium-catalyzed Fujiwara-Moritani-type reaction of unactivated terminal alkenes and benzoic acid derivatives bearing electron donating residues under mild conditions. The acid functionality acts as a traceless directing group delivering products alkenylated in meta-position to the electron donating substituent in contrast to the usually obtained ortho- and para-substitution in Friedel-Crafts-type reactions. Remarkably, the new C−C bond is formed to the C2 of the terminal olefin, in contrast to similar reported transformations. Initially formed mixtures of exo- and endo-double bond isomers can be efficiently isomerized to the more stable endo-products.     

脂肪胺类化合物氨基15N NMR化学位移规律的研究

提出了计算脂肪胺类化合物的¹⁵N NMR化学位移的经验公式：δ_cal（¹⁵N）=-380.2+ΣΔα+ΣΔβ+ΣΔγ+ΣΔδ+ΣC,结合最小二乘法通过线性回归得到了11种取代基参数,计算结果以133种化合物的133个¹⁵N NMR化学位移数据为样本点进行回归检验,置信度为99.5 %,约有94.7 %的¹⁵N NMR化学位移计算值的计算误差小于5.0（相对误差小于0.5 %）.