Bis[(tetraphenylporphyrinato)zinc]-calix[4]pyrrole. Synthesis and receptor properties

A new bis[(tetraphenylporphyrinato)zinc]-calix[4]pyrrole conjugate has been synthesized from monoacetyl-substituted tetraphenylporphyrin, and its complexing ability toward 1,4-diazabicyclo[2.2.2]octane has been evaluated by spectrophotometric titration and 1H NMR spectroscopy.     

双-[2-吡咯(乙氧基)]乙烷的合成及其电化学聚合

以吡咯和二缩三乙二醇为原料合成了N取代吡咯衍生物单体--双-[2-吡咯(乙氧基)]乙烷,并用循环扫描伏安技术研究了该单体的电化学聚合过程.结果表明:在乙腈/高氯酸锂溶液中,双-[2-吡咯(乙氧基)]乙烷在铟锡氧化物导电玻璃(ITO)、Pt、Au、玻璃碳、石墨电极上均能顺利发生反应,形成一定厚度的聚合物膜.但聚合速率、膜的结构、膜的颜色有差异.溶剂水对聚合有明显影响.形成的聚合膜具有良好的电化学稳定性.     

Chiral Bis(tetrathiafulvalene)-1,2-cyclohexane-diamides

Chiral bis(TTF) diamides have been obtained in good yields (54–74%) from 1,2-cyclohexane-diamine and the corresponding TTF acyl chlorides. The (R,R)-1 and (S,S)-1 enantiomers have been characterized by circular dichroism and the racemic form by single-crystal X-ray diffraction. The neutral racemic bis(TTF)-diamide shows the formation of a pincer-like framework in the solid state, thanks to the intramolecular S···S interactions. The chemical oxidation in a solution using FeCl₃ provides stable oxidized species, while the electrocrystallization experiments provided radical cation salts. In particular, single-crystal resistivity measurements on the racemic donor with AsF₆⁻ as a counterion demonstrate semiconductor behavior in this material. The DFT and TD-DFT calculations support the structural and chiroptical features of these new chiral TTF donors.     

Bis(calixcrown)tetrathiafulvalene receptors

A new class of electroactive receptors has been synthesized, built by covalent association of five subunits: two calixarene platforms for spatial organization, two polyether 3D cavities for cation binding, and one electroactive TTF unit to probe the complexation event. Sodium complexation induces rigidification of the molecular assembly, as shown by 1H NMR titration and single-crystal X-ray crystallographic studies on free receptor 14 and a corresponding complex with two bound sodium atoms per receptor (15-(NaPF6)2). The calixarene units in these receptors change from a pinched cone conformation in the free ligand to a symmetrical cone in the complex. Cyclovoltammetric studies validated the electrochemical recognition concept of these five-member assemblies.     

Synthesis and Crystal Structure of Bis[2-[2-(diethylamino)ethyliminomethyl]-4-nitrophenolato]dimethanolcobalt(II) Dinitrate

1 INTRODUCTION The significance of cobalt coordination com- pounds in biological systems is recognized[1～3]. In many instances the cobalt coordination compounds of Schiff bases have been suggested as models to describe energy transfer in naturally occurring systems. In such cases the coordination sphere about the metal ion is believed to play an important role in determining the nature of the model system[4, 5]. In order to investigate the structures of such complexes, we report herein t…     

Synthesis and Crystal Structure of Bis[2-[2-(diethylamino)ethyliminomethyl]-4-nitrophenolato]dimethanolcobalt(Ⅱ) Dinitrate

The title mononuclear cobalt(Ⅱ) complex [Co(DENP)2(MeOH)2]·2NO3 (DENP =2-[2-(diethylamino)ethyliminomethyl]-4-nitrophenolate) was prepared and characterized by elemental analysis, IR and single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group Pī with a = 8.297(1), b = 11.075(2), c = 11.134(2) (A), α = 69.69(1),β = 70.97(2), γ =84.02(2)°, Z = 1, V = 907.0(4) (A)3, Dc = 1.424 g/cm3, Mr = 777.66, λ(MoKα) = 0.71073 (A), μ = 0.548mm-1, F(000) = 409, R = 0.0628 and wR = 0.1734. The complex consists of a [Co(DENP)2-(MeOH)2]2+ cation and two disordered nitrate anions. The Co atom, lying at the inversion centre, is six-coordinated by two DENP ligands and two MeOH molecules in an octahedral geometry. The molecules in the crystal are linked through intermolecular O-H…O, O-H…N and N-H…O hydrogen bonds, forming chains parallel to the b axis.     

Crown-6-calix[4]arene-capped calix[4]pyrrole: an ion-pair receptor for solvent-separated CsF ions

An ion-pair receptor, 1, containing both cation- and anion-recognizing sites, has been synthesized and characterized. Single-crystal X-ray diffraction structural studies and (1)H NMR spectroscopic analyses confirmed that 1 forms stable 1:1 complexes with CsF in solution and in the solid state in spite of the large separation enforced between the receptor-bound anion and cation. In 9:1 CDCl3/CD3OD, binding of fluoride anion within the calix[4]pyrrole core of 1 was not observed in the absence of a cobound cesium cation; however, it was seen in this solvent mixture under conditions where a Cs(+) cation was bound to the crown ether-strapped calix[4]arene subunit.