Acetyl Methyl Torsion in N‐Ethylacetamide: A Challenge for Microwave Spectroscopy and Quantum Chemistry

The gas‐phase structures and parameters describing acetyl methyl torsion of N‐ethylacetamide are determined with high accuracy, using a combination of molecular beam Fourier‐transform microwave spectroscopy and quantum chemical calculations. Conformational studies at the MP2 level of theory yield four minima on the energy surface. The most energetically favorable conformer, which possesses C₁ symmetry, is assigned. Due to the torsional barrier of 73.4782(1) cm^?1 of the acetyl methyl group, fine splitting up to 4.9 GHz is found in the spectrum. The conformational structure is not only confirmed by the rotational constants, but also by the orientation of the internal rotor. The ¹⁴N quadrupole hyperfine splittings are analyzed and the deduced coupling constants are compared with the calculated values.     

Uniform Reduction of Scalar Coupling by Real‐Time Homonuclear J‐Downscaled NMR

Scalar coupling in proton NMR spectra provides important information for the structural analysis. However, the low resolution due to the resulting signal splitting, together with the rather narrow spectral range of hydrogen, often prevents the extraction of J‐coupling information. Here we present a method to achieve real‐time homonuclear J‐downscaling. Thereby, all J‐values are uniformly reduced by an arbitrary scaling factor. In the resulting one‐dimensional spectra, signal overlap is reduced, while scalar coupling information is still available.     

Mixed Linker Metal Organic Framework as an Efficient and Reusable Catalyst for Suzuki Miyaura Coupling Reaction

Series of metal organic frameworks from nitrogen based ligand were synthesized as efficient and reusable catalyst via mixed linker methods. The thermogravimetric study of the mixed linker metal organic framework (MIXMOF) reveals that the complexes are potential thermally stable materials. The palladium supported catalysts exhibits high catalytic activity toward the Suzuki-Miyaura cross coupling reaction and can be reused several times without any visible loss of activity even after five consecutive times.     

Synchronization of complex networks with time‐varying inner coupling and outer coupling matrices

Synchronization of complex networks with time‐varying coupling matrices is studied in this paper. Two kinds of time‐varying coupling are taken into account. One is the time‐varying inner coupling in the node state space and the other is the time‐varying outer coupling in the network topology space. By respectively setting linear controllers and adaptive controllers, time‐varying complex networks can be synchronized to a desired state. Meanwhile, different influences of the control parameters of linear controllers and adaptive controllers on the synchronization have also been investigated. Based on the Lyapunov function theory, we construct appropriate positive‐definite functions, and several sufficient synchronization criteria are obtained. Numerical simulations further illustrate the effectiveness of conclusions. Copyright © 2017 John Wiley & Sons, Ltd.     

Gold‐Catalyzed Suzuki Coupling of ortho‐Substituted Hindered Aryl Substrates

A method that allows hindered ortho ‐substituted aryl iodides to be efficiently coupled to phenylboronic acid using a gold‐catalyzed C−C bond formation is presented. The use of a molecularly‐defined dinuclear gold chloride catalytic precursor that is stabilized by a new tetradentate (N ,N′ )‐diamino‐(P,P′ )‐diphosphino ferrocene hybrid ligand in a Suzuki‐type reaction is described for the first time. Electron‐rich isopropyl groups on phosphorus were found essential for a superior activity, while the performances of a set of analogous gold dinuclear complexes that were fully characterized by multinuclear NMR spectroscopy and XRD analysis, were investigated. Therefore, arylation of para and ortho ‐substituted iodoarenes bearing electron‐rich, electron‐poor functional groups, and even hindered polycyclic aromatic compounds is described.     

Coherent Exciton-Phonon Coupling in CdSe/ZnS Nanocrystals Studied by Two-Dimensional Electronic Spectroscopy

Coherent exciton-phonon coupling in CdSe/ZnS nanocrystals have been investigated by temperature-dependent two-dimensional electronic spectroscopy (2DES) measurements. Benefiting from the ability of 2DES to dissect assembles in nanocrystal films, we have clearly identified experimental evidences of coherent coupling between exciton and phonon in CdSe/ZnS nanocrystals. In time domain, 2DES signals of excitonic transitions beat at a frequency resonant to a longitudinal optical phonon mode; in energy domain, phonon side bands are distinct at both Stokes and anti-Stokes sides. When temperature increases, phonon-induced exciton dephasing is observed with dramatic broadening of homogeneous linewidth. The results suggest exciton-phonon coupling is essential in elucidating the quantum dynamics of excitonic transitions in semiconductor nanocrystals.     

Tetrabutylammonium Salts of Aluminum(III) and Gallium(III) Phthalocyanine Radical Anions Bonded with Fluoren‐9‐olato− Anions and Indium(III) Phthalocyanine Bromide Radical Anions

Reduction of aluminum(III), gallium(III), and indium(III) phthalocyanine chlorides by sodium fluorenone ketyl in the presence of tetrabutylammonium cations yielded crystalline salts of the type (Bu₄N⁺)₂[M^III(HFl−O⁻)(Pc^.3−)]^.−(Br⁻) ⋅ 1.5 C₆H₄Cl₂ [M=Al ( 1 ), Ga ( 2 ); HFl−O⁻=fluoren‐9‐olato⁻ anion; Pc=phthalocyanine] and (Bu₄N⁺) [In^IIIBr(Pc^.3−)]^.− ⋅ 0.875 C₆H₄Cl₂ ⋅ 0.125 C₆H₁₄ ( 3 ). The salts were found to contain Pc^.3− radical anions with negatively charged phthalocyanine macrocycles, as evidenced by the presence of intense bands of Pc^.3− in the near‐IR region and a noticeable blueshift in both the Q and Soret bands of phthalocyanine. The metal(III) atoms coordinate HFl−O⁻ anions in 1 and 2 with short Al−O and Ga−O bond lengths of 1.749(2) and 1.836(6) Å, respectively. The C−O bonds [1.402(3) and 1.391(11) Å in 1 and 2 , respectively] in the HFl−O⁻ anions are longer than the same bond in the fluorenone ketyl (1.27–1.31 Å). Salts 1 – 3 show effective magnetic moments of 1.72, 1.66, and 1.79 μ_B at 300 K, respectively, owing to the presence of unpaired S= 1/2 spins on Pc^.3−. These spins are coupled antiferromagnetically with Weiss temperatures of −22, −14, and −30 K for 1 – 3 , respectively. Coupling can occur in the corrugated two‐dimensional phthalocyanine layers of 1 and 2 with an exchange interaction of J /k _B=−0.9 and −1.1 K, respectively, and in the π‐stacking {[In^IIIBr(Pc^.3−)]^.−}₂ dimers of 3 with an exchange interaction of J /k _B=−10.8 K. The salts show intense electron paramagnetic resonance (EPR) signals attributed to Pc^.3−. It was found that increasing the size of the central metal atom strongly broadened these EPR signals.     

[n]Cyclo‐3,6‐phenanthrenylenes: Synthesis,Structure, and Fluorescence

Five congeners of [n ]cyclo‐3,6‐phenanthrenylene with 3, 4, 5, 7, and 8 panels were obtained from one‐pot macrocyclization of dibromophenanthrene, and their crystal structures with diverse molecular shapes were revealed by X‐ray crystallography. The compounds, except the four‐panel congener, were highly fluorescent in solution, with quantum yields up to 85 %. The least fluorescent four‐panel congener showed the smallest change in its absorption spectrum from that of monomeric phenanthrene, which provided an interesting structure–activity relationship for fluorescent macrocycles to guide future studies.     

Unambiguous Determination of Protein Arginine Ionization States in Solution by NMR Spectroscopy

Because arginine residues in proteins are expected to be in their protonated form almost without exception, reports demonstrating that a protein arginine residue is charge‐neutral are rare and potentially controversial. Herein, we present a ¹³C‐detected NMR experiment for probing individual arginine residues in proteins notwithstanding the presence of chemical and conformational exchange effects. In the experiment, the ¹⁵N^η and ¹⁵N^ϵ chemical shifts of an arginine head group are correlated with that of the directly attached ¹³C^ζ. In the resulting spectrum, the number of protons in the arginine head group can be obtained directly from the ¹⁵N–¹H scalar coupling splitting pattern. We applied this method to unambiguously determine the ionization state of the R52 side chain in the photoactive yellow protein from Halorhodospira halophila . Although only three H^η atoms were previously identified by neutron crystallography, we show that R52 is predominantly protonated in solution.     

光催化剂活性位点调控及其光还原CO2制C2 产物研究进展

工业发展与人类活动导致大气中CO₂浓度逐年升高, 引发一系列生态环境问题. 将CO₂光催化转化为高附加值化学物质不仅有利于缓解环境压力,也可以带来额外经济价值. 然而, 由于多电子利用效率低和C―C偶联动力学缓慢, 光还原CO₂制多碳产品面临产率低和选择性差等挑战. 光催化剂活性位点调控能够有效解决上述问题. 我们综述了近几年用于光还原CO₂催化剂表面活性位点设计的研究进展, 主要包括缺陷位点、 金属位点以及掺杂位点等, 从活性位点的角度为光还原CO₂催化剂设计提供新视角, 并对开发高效光催化剂具有启发意义.