Synthesis, crystal structure and equilibrium studies on the bidentate amine adducts of bis(S-methyl-β-N-(4-methyloxyphenyl) methylendithiocarbazide)nickel(II) complex

The crystal structure of the 1,10-phenanthroline bis(S-methyl-β-N-(4-methyloxyphenyl)methylendithiocarbazide)nickel(II) adduct, (Ni(SN)₂phen) [SN = S-methyl-β-N-(4-methyloxyphenyl)methylendithiocarbazide, PHEN = phenanthroline], has been determined by single crystal X-ray diffraction. The nickel atom is in an octahedral environment, surrounded by two chelating SN ligands and one chelating phen molecule. The nitrogen atoms from phen are in the cis configuration. The other chelating diamines adducts of the parent complex (Ni(SN)₂) were also studied, where the chelating diamnies are 5-nitro-1,10-phenanthroline(NO₂phen), 2,2′-bipyridine (bipy), 4,4′-methyl-2,2′-bipyridine (Mebipy). The equilibria were determined by UV-vis spectrometry in dichloromethane. The coordination ability of the added ligands were influenced by substitute groupings and steric factors. From the structure and addition equilibrium studies, the possible addition mechanisms are also discussed.     

丙烯腈的悬浮聚合

<正> 适用于普通溶液纺丝加工成形的聚丙烯腈(PAN)的分子量一般在5—8万范围内,近年来发展起来的冻胶纺丝方法使得(?)>4.0×10~5的超高分子量PAN也可以纺丝成形,成为制备高强高模PAN纤缎的有效方法之一。随着PAN材料应用领域的开拓,合成超高分子量的PAN是一个首要解决的问题。     

汞—钯试剂络合物极谱吸附波的研究

在极谱催化波和吸附波方面,国内进行了大量的研究,但汞的络合物吸附波至今未见报道。钯试剂已用于光度法测定钯等。我们在研究该试剂与金属离子络合的极谱行为时发现,在硼砂介质中,试剂与Hg~(2+)可形成电活性络合物并可用于汞的测定。     

Charge transport properties of tris(8-hydroxyquinolinato)aluminum(III): why it is an electron transporter

The charge transport properties of mer-tris(8-hydroxyquinolinato)aluminum(III) (mer-Alq), which is the most widely used electron transport material in OLED, were investigated by quantum chemistry calculations within the framework of the charge hopping model and Marcus electron transfer theory. Internal reorganization energies of 0.276 and 0.242 eV were calculated by the DFT-B3LYP method employing a 6-31 G* basis set for the electrons lambdai(e) and holes lambdai(h), respectively. The relative distances and orientations of Alq molecules in amorphous film were simulated by those in the beta-phase. The intermolecular charge-transfer integrals, Hda(h) and Hda(e), along all 14 hopping pathways were then calculated by the Koopmans Theorem in conjunction with the Hartree-Fock method employing a 6-31 G* basis set as well as by the direct coupling method. The results showed that there were some Hda(e) that were 1 order of magnitude larger than any Hda(h), because hopping pathways with effective overlaps of LUMOs can occur and, thus, large Hda(e). On the other hand, effective overlap of HOMO was absent in all pathways, resulting in a relatively small Hda(h). This difference in the magnitudes of Hda(e) and Hda(h) would predict a 2 orders of magnitude difference in the electron-transfer rate constants and account for the observed 2 orders of magnitude difference in the mobilities of electrons and holes.     

智能型水凝胶

智能型水凝胶是一类具有广泛应用前景的功能高分子材料，但由于传统水凝胶存在一些缺点因而限制了其应用，因此近年来围绕提高传统水凝胶的性能做了大量研究工作。本文从四个主要方面综述了近年来智能型水凝胶改性的研究进展。     

同步荧光光谱分析中几个问题的探讨

通过实验阐明了同步荧光光谱与普通荧光光谱之间的关系，在此基础上讨论了溶剂散射光对同步荧光分析的影响以及同步荧光分析的灵敏度。     

INFLUENCE OF DIALKYLZINC IN RARE-EARTH TERNARY CATALYST ON THE COPOLYMERIZATION OF CARBON DIOXIDE AND PROPYLENE OXIDE

Rare-earth ternary catalysts Y（CCl3COO）3-ZnR2-glycerin were prepared for the copolymerization of carbon dioxide and propylene oxide （PO）, where dialkylzincs （ZnR2） were diethylzinc, di（n-propyl）zinc, di（n-butyl）zinc, di（i-propyl）zinc, di（i-butyl）zinc, di（s-butyl）zinc,respectively. The Y（CCl3COO）3-ZnR2-glycerin catalysts displayed the highest catalytic activity at the molar ratio of Y（CCl3COO）3：ZnR2：glycerin = 1：20：10. In the same copolymerization condition, catalysts containing dialkylzincs with branched alkyl group showed lower catalytic activity than that with primary alkyl group. For those catalysts including dialkylzincs with primary alkyl group, their catalytic activity decreases with increasing number of carbon atom in the alkyl group with the following sequence： Y（CCl3COO）3-ZnEt2-glycerin 〉 Y（CCl3COO）3-Zn（n- Pr）2-glycerin〉Y（CCl3COO）3-Zn（n-Bu）2-glycerin. However, the alkyl group in the dialkylzinc does not influence the insertion of PO into the propagation chain end.     

[M(en)3] (ndt)•H2O的水热合成、晶体结构和光学性能 ( M=NiⅡ, CoⅡ, MnⅡ and ndt=1,5-naphthalenedithiolate )

水热条件下，合成了三个新的配合物[Ni(en)₃] (ndt) ·H₂O 1, [Co(en)₃] (ndt) ·H₂O 2 和[Mn(en)₃] (ndt) ·H₂O 3。晶体结构通过X-射线单晶衍射进行了表征。三个配合物均属于单斜晶系，Cc空间群。[M(en)₃]²⁺阳离子、ndt阴离子和结晶水分子通过氢键自组装出相同结构的三维网。通过紫外-可见-近红外漫反射光谱对这三个配合物的光吸收性能和能带进行了测定。     

[Cu(C8H4F3O2S)2(C12H8N2)]·C3H6O的合成及其晶体结构

标题配合物 [Cu(C8H4 F3O2 S) 2 (C12 H8N2 ) ]·C3H6 O属于三斜晶系 ,空间群为P1,并测得如下晶胞参数a =10 .5 77(3) ,b =15 .72 2 (4) ,c =10 .133(2 ) ,α =94 .5 3(2 ) ,β =10 0 .81(2 ) ,γ =96 .18(2 )° ,V =16 37.0 3 3,Z =2 ,Mr =74 4.18,Dx =1.5 1× 10 6 g·m- 3,F(0 0 0 ) =5 2 6 ,μ =8 2 4cm- 1,最终偏差因子为R =0 .0 83,Rw=0 .0 74。Cu(II)与 2个 4 ,4 ,4 三氟 1 (2 噻吩基 )丁二酮 1,3中的四个氧原子和菲咯啉中的两个氮原子 ,组成了一个畸变的八面体构型。     

2020 Roadmap on two-dimensional nanomaterials for environmental catalysis

This roadmap demonstrates a series of two-dimensional nanomaterials, such as graphene, black phosphorus, oxides, layered double hydroxides, chalcogenides, bismuth-based layered compounds, MXenes, metal organic frameworks, covalent organic frameworks, and others, for environmental catalysis.