木质素模化物键离解能的理论研究

采用密度泛函理论B3P86方法,在6-31G(d,p)基组水平上,对木质素结构中的6种连接方式(β-O-4、α-O-4、4-O-5、β-1、α-1、5-5)的63个木质素模化物的醚键(C-O)和C-C键的键离解能E_B进行了理论计算研究。分析了不同取代基对键离解能的影响以及键长与键离解能的相关性。计算结果表明,C-O键的键离解能通常比C-C键的小,在各种醚键中C_α-O键的平均键离解能最小,为182.7 kJ/mol;其次是β-O-4连接中的C_β-O键,苯环和烷烃基上的取代基对醚键的键离解能有较强的弱化作用,C-O键的键长和键离解能的相关性较差。与C-O键相比,C-C键的键离解能受苯环上取代基的影响很小,而烷烃基上的取代基对C-C键的键离解能有较大的影响,C-C键的键离解能和键长之间存在较强的线性关系,C-C键的键长越长,其键离解能越小。     

Altering the Position of Phenyl Substitution to Adjust Film Morphology and Memory Device Performance

In this study, two structural isomers α‐PBT and β‐PBT, which only differ in the phenyl substituent position on the quinoline chromophore, have been designed and successfully synthesized. The influences of substituent position on the film morphology and the storage performance of the devices were investigated. Both molecules employed in the memory devices exhibited same nonvolatile binary (write‐once‐read‐many‐times; WORM) characteristics, but the switch threshold voltage (Vth) of the β‐PBT‐based device was clearly lower than that of the α‐PBT‐based device. Simulation results demonstrate that the variation of the phenyl substituent position led to different intermolecular stacking styles and thus to varied grain sizes for each film morphology. This work illustrates that altering the phenyl substituent position on the molecular backbone could improve the quality of the film morphology and reduce power consumption, which is good for the rational design of future advanced organic memory devices (OMDs).     

重氮化制备钯(0)催化剂及其用于合成芳香胺研究

以2,3-二氨基萘为配体,K_2PdCl_4为金属前驱体,经重氮化制备出一种Pd(0)纳米催化剂(Pd-NPs),其结构经TEM、 XPS、 XRD、 EA和ICP-OES表征,并将催化剂应用于芳香醛类化合物直接还原胺化反应中.在常温常压下以苯甲醛为底物,水为溶剂,H_2为还原剂,探究了胺源、溶剂pH、催化剂用量、反应时间等变量对芳香伯胺产率的影响.实验结果表明芳香伯胺产率高达99%,且该催化剂能多次使用而不失活.     

Selective adsorption behaviors of guest molecules COR in the hexamer host networks at liquid/solid interface

Here,the selective adsorption behaviors of guest molecule COR in two hexamer host grids were investigated by means of scanning tunnelling microscope(STM).The assembled structures of small functional organic molecules TTBTA and TATBA were thermodynamically stable.Interestingly,the introduction of the guest molecule COR destroyed the original hexamer structure of TTBTA and combined with it to form a new triangular host-guest system.Different from TTBTA,the introduction of the guest molecule COR did not affect the six-membered ring structure of TATBA.Furthermore,the co-assembly structure of TTBTA/TATBA/COR was established and the guest molecule COR showed preferential adsorption to the TATBA host grid.Density functional theory(DFT) calculations had been performed to disclose the mechanism of the involved assemblies.     

Novel chiral multidentate P3N4-type ligand for asymmetric transfer hydrogenation of aromatic ketones

Novel chiral multidentate P₃N₄-type ligand has been synthesized and characterized by NMR and HRMS. Using i-PrOH as solvent and hydrogen source, asymmetric transfer hydrogenation of various ketones was investigated. The catalyst generated in situ from chiral multidentate aminophosphine ligand (R,R,R,R)-3 and IrCl(CO)(PPh₃)₂ exhibited highly catalytic activity and excellent enantioselectivity under mild conditions, achieving the corresponding chiral alcohols with up to 99% yield and 99% ee.     

Bay区取代苝二酰亚胺分子构型及聚集调控:邻位甲基位阻效应

设计并合成了2种苝二酰亚胺分子PBI1和PBI2,研究了bay区的苯氧基团邻位甲基取代对分子构型及分子聚集的影响.通过对单晶结构的分析,发现邻位甲基的引入明显影响苝二酰亚胺分子构型,使得4个苯氧基呈中心对称分布.由于甲基的空间位阻效应,有效地减弱了分子间π-π相互作用,从而提高了分子的溶解性与溶液加工成膜性.研究结果表明,在π共轭分子结构中的关键位置引入小的甲基取代基能够显著调控分子的聚集行为,有效减少光电材料分子中非光电活性(增溶性基团)的含量,对光电材料分子的设计合成具有重要的指导意义.     

Efficient synthesis of N-nosyl-protected 3-azabicyclo[4.3.0]nonen-8-one by an aniline- and nitrobenzene-mediated Pauson–Khand cyclization

The intramolecular Pauson–Khand cyclization in the presence of both aniline and nitrobenzene was used to improve the construction of N-nitrobenzenesulfonyl-protected 3-azabicyclo[4.3.0]nonane skeletons. We found that aniline enhanced the cyclization and that nitrobenzene prevents the concurrent reduction in this process. This combination of mediators allows for the efficient synthesis of bioactive azabicyclic nonane-type alkaloids and the use of milder deprotection conditions in the synthetic route.     

Numerical Investigation on 1,3-Butadiene/Propyne Co-pyrolysis and Insight into Synergistic Effect on Aromatic Hydrocarbon Formation

A numerical investigation on the co-pyrolysis of 1,3-butadiene and propyne is performed to explore the synergistic effect between fuel components on aromatic hydrocarbon formation.A detailed kinetic model of 1,3-butadiene/propyne co-pyrolysis with the sub-mechanism of aromatic hydrocarbon formation is developed and validated on previous 1,3-butadiene and propyne pyrolysis experiments.The model is able to reproduce both the single component pyrolysis and the co-pyrolysis experiments,as well as the synergistic effect between 1,3-butadiene and propyne on the formation of a series of aromatic hydrocarbons.Based on the rate of production and sensitivity analyses,key reaction pathways in the fuel decomposition and aromatic hydrocarbon formation processes are revealed and insight into the synergistic effect on aromatic hydrocarbon formation is also achieved.The synergistic effect results from the interaction between 1,3-butadiene and propyne.The easily happened chain initiation in the 1,3-butadiene decomposition provides an abundant radical pool for propyne to undergo the H-atom abstraction and produce propargyl radical which plays key roles in the formation of aromatic hydrocarbons.Besides,the 1,3-butadiene/propyne co-pyrolysis includes high concentration levels of C3 and C4 precursors simultaneously,which stimulates the formation of key aromatic hydrocarbons such as toluene and naphthalene.     

Substituent Effects on EI-MS Fragmentation Patterns of 5-Allyloxy-1-aryl-tetrazoles and 4-Allyl-1-aryl-tetrazole-5-ones; Correlation with UV-Induced Fragmentation Channels

1,4- and 1,5-disubstituted tetrazoles possess enriched structures and versatile chemistry, representing a challenge for chemists. In the present work, we unravel the fragmentation patterns of a chemically diverse range of 5-allyloxy-1-aryl-tetrazoles and 4-allyl-1-aryl-tetrazolole-5-ones when subjected to electron impact mass spectrometry (EI-MS) and investigate the correlation with the UV-induced fragmentation channels of the matrix-isolated tetrazole derivatives. Our results indicate that the fragmentation pathways of the selected tetrazoles in EI-MS are highly influenced by the electronic effects induced by substitution. Multiple pathways can be envisaged to explain the mechanisms of fragmentation, frequently awarding common final species, namely arylisocyanate, arylazide, arylnitrene, isocyanic acid and hydrogen azide radical cations, as well as allyl/aryl cations. The identified fragments are consistent with those found in previous investigations concerning the photochemical stability of the same class of molecules. This parallelism showcases a similarity in the behaviour of tetrazoles under EI-MS and UV-irradiation in the inert environment of cryogenic matrices of noble gases, providing efficient tools for reactivity predictions, whether for analytical ends or more in-depth studies. Theoretical calculations provide complementary information to articulate predictions of resulting products.     

Cu2O-Catalyzed Conversion of Benzyl Alcohols Into Aromatic Nitriles via the Complete Cleavage of the C≡N Triple Bond in the Cyanide Anion

Nitrogen transfer from cyanide anion to an aldehyde is emerging as a promising method for the synthesis of aromatic nitriles. However, this method still suffers from a disadvantage that a use of stoichiometric Cu(II) or Cu(I) salts is required to enable the reaction. As we report herein, we overcame this drawback and developed a catalytic method for nitrogen transfer from cyanide anion to an alcohol via the complete cleavage of the C≡N triple bond using phen/Cu₂O as the catalyst. The present condition allowed a series of benzyl alcohols to be smoothly converted into aromatic nitriles in moderate to high yields. In addition, the present method could be extended to the conversion of cinnamic alcohol to 3-phenylacrylonitrile.