A Novel 3‐D Heterobimetallic Cyano‐bridged Coordination Polymer Incorporating Ag···Ag Interaction: [Cu(dien)Ag(CN)2]2[Ag2(CN)3][Ag(CN)2]

A three‐dimensional cyano‐bridged copper(II) complex, [Cu(dien)Ag(CN)₂]₂[Ag₂(CN)₃][Ag(CN)₂] ( 1 ) (dien = diethylenetriamine), has been prepared and characterized by X‐ray crystallography. Complex 1 crystallized in the monoclinic space group P2₁/n with a = 6.988(2), b = 17.615(6), c = 12.564(4) Å, β = 90.790(5)°. The crystal consists of cis‐[Cu(dien)]²⁺ units bridged by [Ag(CN)₂]^— to form a zig‐zag chain. The Ag atoms of the free and bridging [Ag(CN)₂]^— link together to form additional infinite zig‐zag chains with short Ag···Ag distances. The presence of Ag···Ag interactions effectively increases the dimensionality from a 1‐D chain to a 3‐D coordination polymer.     

A Novel Fluorescent Aminoacid Designed for Fluorometric Detection of Cu （Ⅱ）

A fluorescent aminoacid was designed for selective and sensitive detection of Cu(II) in aqueous solution. The designing of this Cu(II) fluorescent chemosensing molecule, N ± (1‐naphthyl). aminoacetic acid (NAA), was based on the binding of Cu(II) to aminoacetic acid and the novel charge transfer photophysics of 1‐aminonaphthalenes. The fluorescence of NAA was found quenched by Cu (II) and several other metal ions of similar electronic structure such as Co(II), Ni(II) and Zn(II). The quenching was shown to occur via electron transfer within the metal‐NAA complex, which required an optimal combination of high binding affinity and favorable redox properties of the components in the metal‐NAA complex and hence afforded selective fluorometric detection of Cu(II). The calibration graph obeyed Stern‐Volmer theory and was shown for Cu(II) over the range of 0–2.75 ± 10–⁴ mol/L. The quenching constant of Cu(II) was measured as 8.0 ± 10³ mol/L that was two orders of magnitude higher than those of Co(II), Ni(II) and Zn(II). The 3SD limit of detection for Cu(II) was 8.00 ± 10^?6 mol/L with a coefficient of variation of 1.65%. Linear range for quantitative detection of Cu(II) was 2.67 ± 10^?5‐2.75 ± 10^?4 mol/L. The method was applied to synthetic sample measurements which gave recoveries of 105%‐112%.     

Anion and Additive Effects on the Structure of Mercury(II) Halides Complexes with Tripodal Ligand

The metal complexes [Hg₂(tbim)₂Br₄]·2DMF ( 1 ) and [Hg₂(tbim)I₄]·1.5DMF ( 2 ) were prepared by reactions of 1,3,5‐tris(benzimidazol‐1‐ylmethyl)‐2,4,6‐trimethylbenzene (tbim) with HgBr₂, HgI₂, respectively, and [Hg₂(tbim)I₄]·0.5(FeCp₂)·H₂O ( 3 ) was obtained by the same method with addition of ferrocene (FeCp₂) as additive. Their structures were determined by X‐ray crystallographic analyses. Complex 1 has a macrocyclic binuclear structure with one benzimidazole arm of the ligand free of coordination and the binuclear units are further connected by C‐H···N hydrogen bonds to give an infinite zigzag chain. Complexes 2 and 3 have a 2D network structure in which tbim serves as a tridentate ligand. The results showed that the halides of bromide and iodide have remarkable impact on the structure of the complexes. The FeCp₂ molecules are trapped in the voids of framework 3 .     

Synthesis and Investigation of Soluble Polymer-supported Dendrimers

Poly（ethylene glycol） （PEG）-supported dendrimers have been synthesized using 2.4,6-trichloro-1,3,5-triazine （TCT） as dendrons and tris（hydroxymethyl）aminomethane as tinkers with high loading capacity, excellent solubility and thermal stability by divergent method. The new synthesized PEG-supported G2.0 dendrimer has 10 times as large functional group loading capacity as commercial PEG3400 with overall yield 44.0%.     

Inside Cover: From Reactivity and Regioselectivity to Stereoselectivity: An Odyssey of Designing PIP Amine and Related Directing Groups for C—H Activation (Chin. J. Chem. 7/2019)

The inside cover picture shows the journey of developing PIP amine directing group for C—H activation, from controlling the reactivity and diastereoselectivity to enantioselectivity. In the presence of Pd or base metal catalysts, PIP amine enabled the activation of inert C—H bonds to form diverse C—C and C—heteroatom bonds. Its tuneable structure has triggered the design of chiral auxiliaries for diastereoselective C—H activation. More recently, enantioselective activation of unbiased methylene C—H bonds has been achieved by cooperative effects between PIP amine and axial chiral ligands. More details are discussed in the article by Shi et al. on page 647–656.

     

Synthesis and characterization of meso-ferrocenylethynyl 5,15-diphenylporphyrins

A series of four meso-ferrocenylethynyl (5,15-diphenylporphyrinato)nickel(II) derivatives have been synthesized by Sonogashira coupling reactions. Three of these compounds contain the electron-withdrawing groups including -CHO, -CHC(CN)₂, and -CCC₆H₄NO₂ at the remaining meso position, with a view to preparing push-pull chromophores, in which ferrocene serves as the electron donor. All the new compounds have been characterized spectroscopically and the molecular structure of one of these porphyrins (compound 11) has also been determined. The studies show that although the ferrocenylethynyl group can extend the π system of the central porphyrin core, the cyclopentadienyl rings of ferrocene are almost orthogonal to the porphyrin ring. This hinders ferrocene serving as a good electron donor in these systems.     

Electrochemical Study of Indium in a Water‐Stable 1‐Ethyl‐3‐Methylimidazolium Chloride/Tetrafluoroborate Room Temperature Ionic Liquid

The electrochemistry of indium species was investigated at glassy carbon, tungsten and nickel electrodes in a basic 1‐ethyl‐3‐methylimidazolium chloride/tetrafluoroborate ionic liquid. Amperometric titration experiments suggest that In(III) chloride is complexed as [InCl₅]^2? in this ionic liquid. The electrochemical reduction of [InCl₅]^2? to indium metal is preceded by overpotential driven nucleations. The effective anodic dissolution of indium to indium(III) requires, however, the presence of sufficient chloride ions at the electrode surface. The electrodeposition of indium at glassy carbon and tungsten electrodes proceeds via three‐dimensional instantaneous nucleation with diffusion‐controlled growth of the nuclei. At the nickel electrode, the deposition proceeds via three‐dimensional progressive nucleation with diffusion‐controlled growth of the nuclei. Raising the deposition temperature decreases the average radius of the individual nuclei, r. Scanning electron microscopic and x‐ray diffraction data indicated that bulk crystalline indium electrodeposits could be prepared on nickel substrates within a temperature range between 30 and 120 °C.     

1,3‐dipolar cycloaddition reactions of nitrile oxides to prop‐1‐ene‐1,3‐sultone

The reaction of prop‐1‐ene‐1,3‐sultone 1 with a variety of nitrile oxides 3 afforded novel [3+2] cycloaddition products 4 in good yield. The cycloaddition reaction achieved excellent regioselectivity.     

CoCl_2·6H_2O or LaCl_3·7H_2O Catalyzed Biginelli Reaction. One-Pot Synthesis of 3,4-Dihydropyrimidin-2(1 H)-ones

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On-line coupling of capillary isoelectric focusing with transient isotachophoresis-zone electrophoresis: a two-dimensional separation system for proteomics

A microdialysis junction is employed as the interface for on-line coupling of capillary isoelectric focusing with transient isotachophoresis-zone electrophoresis in a two-dimensional separation system. Capillary isoelectric focusing not only provides high-resolution separation of tryptic peptides based on their differences in isoelectric point, but also potentially allows the analysis of low-abundance proteins with a typical concentration factor of 50-100 times. Carrier ampholytes, employed for the creation of a pH gradient during focusing, are further utilized as the leading electrolyte in the second separation dimension, transient isotachophoresis-zone electrophoresis. Many peptides which have the same isoelectric point would most likely have different charge-to-mass ratios, and thus different electrophoretic mobilities in zone electrophoresis. Two-dimensional separation of proteolytic peptides is demonstrated using standard proteins, including cytochrome c, ribonuclease A, and carbonic anhydrase II. The maximum peak capacity is estimated to be around approximately 1600 and can be significantly increased by simply increasing the capillary column length and manipulating the range of pH gradient in isoelectric focusing. In addition to enhanced separation efficiency and resolution, this two-dimensional electrokinetic separation system permits sensitive and comprehensive analysis of peptide fragments, especially when integrated with electrospray ionization mass spectrometry for peptide/protein identification.