Synthesis of 2,2′ ∶ 6′, 2″ - Terpyridine Derivative Ligands

以对甲基苯甲醛和2-乙酰吡啶为主要原料,合成了三种2,2′:6′,2″-三联吡啶衍生物配体,并以IR和1HNMR对其结构进行了表征;对影响2-乙酰吡啶和对甲基苯甲醛反应的主要反应条件进行了优化,以20℃下反应24h最佳.     

Synthesis and Self-assembling Properties of 2,2′:6′,2″-Terpyridine-Based Carbon Nanotube Coordination Polymers

A novel metallo-supramolecular polytopic ligand was synthesized from the attachment reaction involving an amino group-functionalized multi-wall carbon nanotube and 4-chloro-2,2′:6′,2″-terpyridine used for the preparation of metallo-supramolecular polymers with Co(II) or Ni(II) ions. Different colors were observed depending on either the ligands or the metal ions in this type of supramolecular assembly. The created supramolecular polymers were characterized by means of structure, morphology, and stimuli-responsive performance employing scanning electron microscopy, amperometric techniques, UV–Vis and Fourier transform infrared spectroscopy. UV–Vis spectroscopy and cyclic voltammetry studies confirmed that both the optical and electrochemical properties of metallo-supramolecular materials are affected by the substituent at the pyridine periphery.     

Nickel complex-mediated copolymerization of regioisomeric 5,5′-bis(chlorobenzoyl)-2,2′-dimethoxybiphenyls: synthesis of wholly aromatic copolyketones

Aromatic coupling copolymerization of 5,5^′-bis(4-chlorobenzoyl)-2,2^′-dimethoxybiphenyl (1) and 5,5^′-bis(3-chlorobenzoyl)-2,2^′-dimethoxybiphenyl (2) has successfully afforded higher-molecular-weight polyketones than either of the corresponding homopolymerizations. The wholly aromatic copolyketones thus obtained have highly amorphous nature with high glass transition temperatures (T_g).     

Photoelectrical properties of the system ITO/poly(4,4″-dipenthoxy-3′-dodecyl-2,2′:5′,2″-terthiophene)/Al: Effect of electrosynthesis conditions

The photoelectrical properties of the system ITO/poly(4,4-dipenthoxy-3-dodecyl-2,2:5,2-terthiophene)/aluminium are strongly dependent on the electrochemical preparation parameters of the polymer. In particular the polymerization temperature has a significant influence on the photoelectronic characteristics of polymer. The best properties were attained with polymers prepared at higher temperatures (32–40 °C).     

Aldehyde-decorated 2,2′-bipyridine and 2,2′:6′,2″-terpyridine ruthenium(II) complexes: Convenient scaffolds for supramolecular chemistry

Two new aldehyde-decorated tpy and bpy-containing ruthenium(II) complexes, [Ru(1)(bpy)₂][PF₆]₂ and [Ru(1)(tpy)Cl][PF₆] in which 1 is 5,5′-bis(4-formylphenyl)-2,2′-bipyridine, have been prepared and fully characterized. The packing in both solid state structures involves extensive O_aldehyde···HC_pyridine contacts, but π-stacking interactions are important only between [Ru(1)(tpy)Cl]⁺ cations.     

First example of a CLICK reaction of a coordinated 4′-azido-2,2′:6′,2″-terpyridine ligand

The first example of a copper-catalysed [2 + 3] cycloaddition reaction of a coordinated 4′-azido-2,2′:6′,2″-terpyridine ligand is reported and the solid state structures of the precursor and product are described.     

对甲苯基-2,2′:6′,2″-三联吡啶的合成方法改进

以2-乙酰吡啶和对甲基苯甲醛为原料,在室温下的乙醇溶液中制得3-(4-甲基苯)-1,5-二(2-吡啶基)-1,5-戊二酮,后者在氢氧化钠存在下与浓氨水反应1 h得到标题化合物,总产率31.7%。与文献相比,反应条件温和,提纯步骤简单。     

Heteroditopic ligands containing a 2,2′-bipyridine and a 2,2′:6′,2″-Terpyridine moiety and their ruthenium tris(bipyridine)-like complexes

Two novel heteroditopic ligands in which the bidentate 2,2^′-bipyridine (bpy) ligand is covalently linked to one or two 2,2^′:6^′,2″-terpyridine (terpy) terdentate ligands have been prepared and characterized. The synthesis and the physico-chemical features of their corresponding complexes in which the bpy site is complexed by a ruthenium moiety are also reported.     

2,2′∶6′,2″-三联吡啶衍生物配体的合成

以对甲基苯甲醛和2-乙酰吡啶为主要原料,合成了三种2,2′：6′,2″-三联吡啶衍生物配体,并以IR和1HNMR对其结构进行了表征;对影响2-乙酰吡啶和对甲基苯甲醛反应的主要反应条件进行了优化,以20℃下反应24h最佳。     

Clicking not cooking: Functionalization of 2,2′:6′,2″-terpyridines by diol–boric acid interactions

A diol–boric acid condensation is a simple type of CLICK reaction that can be applied to give a family of related ligands. It is exemplified by the reaction of 4′-(3,4-dihydroxyphenyl)-2,2′:6′,2″-terpyridine (1) with naphthalene-1-boronic acid. The single crystal structures of 1^.MeOH and [Fe(1)₂][BF₄]₂? 4H₂O?0.2CH₃CN are presented.     

Rapid decolorisation of dyeing wastewater by FeIII(2,2′:6′,2″-terpyridine)activated peroxymonosulphate

The discharge of coloured textile printing and dyeing wastewater causes environmental pollution. Disposing of wastewater efficiently, simply and with low consumption, is a problem that must be addressed. Herein, a catalytic method for rapid decolorisation of organic dyes was devised employing a terpyridine iron complex to activate oxidised permonosulphate. CI Acid Red 1 was used as the simulated pollutant, the influences of operating parameters on the fading effects of wastewater were explored. According to the results, the produced catalytic system exhibits a universal catalytic effect. Even when the dye concentration reaches 76.4 mg/L, the dyeing wastewater may be effectively decolorised. In addition, when anions (HCO₃⁻, SO₄²⁻, Cl⁻) were present in the solution, the degradation effect of CI Acid Red 1 was still effective. Interestingly, active species such as sulphate radicals and singlet oxygen were detected in the catalytic degradation system by radical capture experiments. The removal rate of total organic carbon can achieve a percentage of 26.22% in 2 hours. This research provides a unique, enzyme-like catalytic system for the rapid breakdown of dye contaminants.     

Metal complexes of diaryl and 2,2′-dipyridyl disulfides

The variable transformations of the S?S bond in the presence of metal complexes generally depend upon the different reaction conditions used. In this review, the synthesis and coordination versatility of complexes derived from diaryl and 2,2′ -dipyridyl disulfide have been discussed in the absence or presence of other donor groups.     

Synthesis,structure and characterization of neat Zn2(OH)2 diamond-core chains linked through 2,2′,4,4′-biphenyl-tetracarboxylate

Reaction of 2,2′,4,4′-biphenyltetracarboxylic acid (2,4-H₄bptc), Zn(NO₃)₂ · 6H₂O in the presence of NaOH hydrothermally at 180 °C affords the first 2,4-H₄bptc complex [Zn₃(μ₃-OH)₂(2,4-bptc)]_n · 2nH₂O (1). Crystal structure indicates that 1 is Zn₂(OH)₂ diamond-core chains linked through 2,2′,4,4′-biphenyltetracarboxylate. 1 was characterized by TG, IR and fluorescence spectra. 1 is the first example of 2,4-H₄bptc complex and also first neat Zn₂(OH)₂ diamond-core chains.     

Syntheses and Characterization of Two New M(II)-5,5′-dimethyl-2,2′-bipyridine (M = Cd and Pb) Coordination Polymers and Study of Their Thermal and Electrochemical Properties

Two new cadmium(II) and lead(II)-thiocyanato coordination polymers with 5,5′-dimethyl-2,2′-bipyridine (5,5′-dm-2,2′-bpy) as chelating ligands were synthesized and characterized by elemental analysis, IR and ¹H NMR spectroscopy and by X-ray crystallography. Thermal and electrochemical properties were also studied as well. These complexes have formed formula [Cd(5,5′-dm-2,2′-bpy)(NCS)₂]_n (1) and [Pb(5,5′-dm-2,2′-bpy)(CH₃COO)(NCS)]_n (2). The coordination numbers of Cd^II in 1 and Pb^II in 2 are six (CdN₄S₂) and seven (PbN₃O₃S₂), respectively. In 2, “stereo-chemically active” electron lone pairs and the coordination spheres were hemidirected. Bridging properties of thiocyanato anions in 1 and 2 created one- and two-dimensional coordination polymers, respectively. The supramolecular features in these complexes were guided and controlled by weak directional intermolecular interactions.     

Synthesis and characterization of novel crown ether containg copolymers Ru catalyzed copolymerization of 4′-acetylbenzocrown ethers with α,ω-dienes

Summary Ruthenium catalyzed step growth copolymerization of 4-acetylbenzo-15-crown-5 and 4-acetylbenzo-18-crown-6 and ,-dienes such as 1,3-divinyltetramethyldisiloxane or 3,3,6,6-tetramethyl-3,6-disila-1,7-octadiene give novel copolymers which incorporate crown ethers into the polymer backbone in a regular manner. The synthesis of these thermally stable copolymers and their characterization is reported. Lithium cation crown complexes have been formed.     

Electrorheological properties of poly[N,N′-(2-amino-5-carboxybutyl-1,3-phenylenedimethylene)-2,2′-diamino-4,4′-bithiazole]

Poly[N,N′-(2-amino-5-carboxybutyl-1,3-phenylenedimethylene)-2,2′-diamino-4,4′-bithiazole] was synthesized and characterized with Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). Anhydrous electrorheological (ER) fluids were prepared using the polymer particles as disperse phase and bromodiphenylmethane as a disperse medium. Rheological measurements were carried out via a rotational rheometer to investigate the effects of electric field strength and the polymer particle content on the ER properties. Results indicate that suspensions of the polymer particles containing amino and carboxybutyl groups in bromodiphenylmethane exhibit a substantial ER effect.     

Electrochemical Synthesis of Cu (II) Coordination Polymer Coatings Based on 2,2′-Thiodiacetic Acid and 1,2,4,5-Benzenetetracarboxylate

Electrochemical synthesis of coordination polymers of Cu(II), [Cu(TDA)]_n and [Cu₂(BTC)(H₂O)₆?6H₂O]_n in which H₂TDA is 2,2′-thiodiacetic acid and BTC stands for 1,2,4,5-benzenetetracarboxylate was carried out by the electrochemical oxidation of Cu anode in the presence of H₂TDA (a flexible ligand), and 1,2,4,5-benzentetracarboxylic acid (H₄BTC) (a rigid ligand) in aqueous solutions. The structure of coordination polymers were characterized by scanning electron microscopy, X-ray powder diffraction, elemental analysis, thermal gravimetric and differential thermal analyses. The crystal structure of the compounds consists of one-dimensional cubical crystal polymeric units of [Cu(TDA)]_n and [Cu₂(BTC)(H₂O)₆?6H₂O]_n. Furthermore, the coordination number of Cu (II) ions in synthesized coordination polymers to be found five. The main advantages of electrosynthesis are the minor synthesis time, the milder conditions and the facile synthesis of coordination polymer coatings.     

Cellulose acetate–silica fume membrane: characterization and application for separation of starch and maltose

Maltose is one of the starch derivatives. Maltose can be produced by starch hydrolysis using any kind of hydrolytic process. One of the methods to separate a mixture of both compounds is using porous membrane. In this research, a novel type of hybrid membrane was prepared from a mixture of cellulose acetate and silica fume. Silica fume is widely used in the domain of construction as cement material, whereas in this research silica fume was successfully used as membrane material. Various compositions of membrane dope solutions were prepared for obtaining the membranes used for separation of starch and maltose. Such synthesized membranes demonstrate a good performance in separation processes. The best performance is achieved when the composition of cellulose acetate in membrane dope solution is 15 % (w/w) in N,N-dimethylacetamide solvent and the mass ratio between cellulose acetate and silica fume is 4:1. For this composition, the rejection of membranes towards starch and maltose is 87 and 2 %, respectively, at working pressure of 3 bar and compaction time of 2 h. Infrared spectrum indicates no new peaks are found compared to raw materials’ spectral peaks. Thus, it can be concluded that the interaction between the cellulose acetate and silica fume is merely a physical type. From the observation of cross-sectional SEM images, we can remark that the morphology of such a membrane is porous. X-ray diffractogram indicates that the synthesized membranes are amorphous.