Synthesis and Properties of Functionalized Schiff Bases of 5α,10α-Di（4-hydroxylphenyl）calix[4]pyrrole and 5α,15β-Di（4-hydroxylphenyl）calix｜4] pyrrole

A series of calix[4]pyrrole meso-substituted Schiff bases was synthesized with 5α,10α-di（4- hydroxylphenyl）calix[4]pyrrole or 5α,15β-di（4-hydroxylphenyl）calix[4]pyrrole as starting materials. The synthetic routes included alkylation with methyl a-chlroroaceate, ammonolysis with alkylene diamine, and condensation with salieylladehyde or 2-hydroxynaphthaldehyde. The crystal structures of the new calix[4]pyrroles and their Schiff bases were determined by X-ray diffraction. The coordination properties of the representative ealix[4]pyrrole Sehiff bases to transition metal ions were also investigated by UV-Vis spectra.     

Synthesis and structure characterization of novel calix[4]（aza）crown derivatives

Three novel calix[4](aza)crown deravatives have been synthesized,including a new [2]pseudorotaxane in which calix[4]- azacrown behaves as a stopper,a novel‘tren’type calix[4]azacrown and a novel‘spiro’type calix[4]azacrown containing morpholine unit.The structures of these compounds have been confirmed by NMR and MS.     

Synthesis, structure and anion binding properties of lower rim α-hydroxyamide calix[4]arene derivatives

A new family of p-tert-butylcalix[4]arenes functionalized at the lower rim with α-ketoamide or α-hydroxyamide functions has been prepared. The ¹H and ¹³C NMR spectra indicate that the macrocycles preferably adopt a cone conformation. X-ray crystal study of the α-ketoamide derivative 4a shows the flattened cone conformation in the solid state. Reduction of α-ketoamide 4ab has produced the α-hydroxyamide derivatives 6ab. The introduction of chiral moieties on the lower rim position of the calix[4]arene allowed the synthesis of the chiral derivatives 7 and 8. Host-guest complexation properties towards various anions of the chiral α-hydroxyamide 8 have been examined by ¹H NMR spectroscopy. This new receptor has shown promising selectivity for and N-tosyl-(L)-alaninate.     

Synthesis, crystal structure, and thermal properties of N,N′-di(diethoxythiophosphoryl)-1,4-phenylenediamine

The title compound N,N′-di(diethoxythiophosphoryl)-1,4-phenyl-enediamine was synthesized by the reaction of diethoxythiophosphoryl chloride with p-phenylenediamine and characterized by elemental analysis, IR, and ¹H NMR spectra. Its crystal structure was determined by X-ray diffraction analysis and the thermal property was studied by TG analysis. The relative molecular weight of the title compound is 412.42. The crystal structure belongs to the orthorhombic, Pbca space group, with a = 0.86936(16) nm, b = 1.2787(2) nm, c = 1.8897(3) nm, β = 90°, V = 2.1006(7) nm³, Z = 8, Dc = 1.304 g/cm³, μ(Mo Kα) = 0.425 mm⁻¹, F(000) = 872, S = 1.052, the final R = 0.0628 and wR = 0.1860 for 1852 observed reflections with I>2σ(I). The X-ray diffraction analysis demonstrates that the crystal structure is centrosymmetric. The weak N-H⋯S intramolecular hydrogen bonds were observed to link the molecules into sheets. The TG analysis shows that the title compound has good thermal stability and char forming capability and its fire retardation for polyacrylonitrile reveals that the compound is an excellent intumescent fire retardant. __________ Translated from Acta Chimica Sinica, 2007, 65(18): 2034–2038 [译自: 化学学报]     

Synthesis and mesomorphic properties of calix[4]resorcinarene–triphenylene oligomers

By controlling the mol ratios of reactants, novel calix[4]resorcinarene–triphenylene monomer, dimer and tetramer were designed and synthesised in yields of 50–60% via Click chemistry. Their structures were characterised by NMR and MS. Their liquid crystalline behaviours were studied by differential scanning calorimetry, polarising optical microscopy and X-ray diffraction analysis. The more triphenylene units on calix[4]resorcinarene resulted in the wider temperature scopes of mesophase and higher phase transition temperatures. The monomer 6 and dimer 7 showed the mixed columnar mesophase with hexagonal columnar structure and disordered lamellar columnar structure, and compound 8 possessed only disordered lamellar columnar mesophase. These research results suggest that calix[4]resorcinarene was a good platform to construct columnar liquid crystal and the mesomorphic properties were greatly influenced by the substituted numbers of mesogen units on calix skeleton.     

Synthesis and Conformational Properties of Bis（calix [4] arene）

The bis(calix [4] arene)3 was synthesized in moderate yield by the reaction of p-tert-butylcalix [4] arene (1) with 1,4-bis(chloromethyl) benzene (2). The conformation of all alkylated product 4 was investigated by the variable-temperature ^1H-NMR.     

Synthesis,crystal structure and conformation of N-acetyl-Cα,α-diethylglycine-N′-methylamide

Summary Synthesis and X-ray structure analysis of N-acetyl-^,-diethylglycine-N-methylamide [CH₃-Co-NH-C(C₂H₅)₂-CO-NHCH₃] are described. The compound was obtained from the corresponding N-acetyl derivative [CH₃-CO-NH-C(C₂H₅)₂-COOH] through the mixed anhydride procedure. It crystallizes as monohydrate (C₉H₁₈N₂O₂·H₂O) in space group P2₁/c,a=7.139(1),b=11.823(2),c=15.778(3) Å, =122.23(1)°,V=1126.53 ų,D _m=1.20 Mgm^–3 (room temperature),R=0.046 for 1523 reflections. The crystal packing is dominated by two strong hydrogen bonds between the water molecule and two carbonyl oxygen atoms and two weak H-bonds to two amide-N-atoms of symmetry-equivalent molecules. The molecular conformation is closer to a 3₁₀-helix then ana-helix.

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Synthese, Kristallstruktur und Konformation von N-Acetyl-^,-diethylglycin-N-methylamid

Zusammenfassung Es wird über Synthese und die röntgenographische Strukturbestimmung von N-Acetyl-^,-diethylglycin-N-methyl-amid [CH₃-CO-NH-C(C₂H₅)₂-CO-NH-CH₃] berichtet. Die Verbindung wurde unter Anwendung der Methode der gemischten Anhydride aus dem entsprechenden N-Acetylderivat [CH₃-CO-NH-C(C₂H₅)₂-COOH] erhalten. Sie kristallisiert als Monohydrat (C₉H₁₈N₂O₂·H₂O) in der Raumgruppe P2₁/c mita=7.139(1),b=11.823(2),c=15.778(3) Å, =122.23(1)°,V=1126.53 ų,D _m=1.20 Mgm^–3,D _x=1.204 Mgm^–3 (Raumtemperatur).R=0.046 für 1523 Reflexe. Die Kristallpackung ist dominiert durch zwei starke H-Brücken vom Wassermolekül zu zwei Carbonylsauerstoffatomen sowie zwei schwachen H-Brücken zu zwei Amid-N-atomen symmetrieequivalenter Moleküle. Die Konformation des Peptidgerüstes ist näher einer 3₁₀ als einera-Helix.

     

Synthesis of novel calix[4]crown telomers and selective extraction of cesium ions

p-tert-Butylcalix[4]diazacrown-4 telomer, which contains hard and soft ion binding sites, was synthesized. It exhibited high selectivity toward cesium ions. The binding sites may complex alkali metal ions selectively.     

Synthesis,crystal structure and magnetic properties of [1-(4′-bromobenzyl)-4-methylquinolinium] [Ni(mnt)2] complex (mnt2 − =maleonitriledithiolate)

A new ion-pair complex, [BrBzMeQl][Ni(mnt)₂] (1) ([BrBzMeQl]⁺?=?1-(4′-bromobenzyl)-2-methylquinolinium; mnt^2??=?maleonitriledithiolate), has been prepared and characterized. X-ray diffraction analysis shows that the Ni(mnt)₂ anion and [BrBzMeQl]⁺ cations of 1 form completely segregated stacking columns, with the Ni?···?Ni distances alternating between 3.717 and 4.466?Å?in the Ni(mnt)₂ stacking column. The variable-temperature magnetic susceptibilities of 1 have been measured over the range 75–300?K and the results reveal that the complex exhibits antiferromagnetic behavior.     

Novel Synthesis and Characterization of N‐Substituted‐calix[4]azacrown Derivatives

Novel calix[4]azacrown derivatives from the reaction between calix[4]amidocrown and the different N‐(4‐bromoacetamidephthalimido)alkanes derivatives, which may be useful intemediate compounds of pseudorotaxane, have been synthesized and structurally characterized by IR, ¹H NMR, ¹³C NMR, MS, and elemental analyses. From their analysis data, it was found that compounds 6a–d adopted a cone conformation.     

Synthesis,crystal structure and luminescent properties of two complexes containing [Au(CN)2] − building blocks

Two supramolecular complexes, {{Ni(H₂O)(phen)₂[Au(CN)₂]}[Au(CN)₂]?·?1.5H₂O} _n (1) (phen?=?1,10-phenanthroline) and [H₂teta][Au₂(CN)₄]?·?2H₂O (2) (teta?=?5,7,7,12,14,14-hexamethyl-1,4,8,11-tetra-azacyocloteradeca-4,11-diene) have been synthesized and structurally characterized. Complex 1 was a one-dimensional infinite chain constructed by [Au(CN)₂]^? building blocks. In complex 2, there are one cation, one anion, and two water molecules in the asymmetric unit. The two complexes are interconnected through a combination of aurophilic attractions and hydrogen bonds and formed into 3D supramolecular structures. The aqueous solutions of 1 and 2 display interesting luminescence at room temperature.     

Synthesis and crystal structure of dinuclear nickel (Ⅱ) complex

The crystal structure of Ni(Ⅱ) complex with 3-hydroxyl-1, 5-diazacycloheptane-N, N'-diacetate was determined by X-ray diffraction method. Crystal data for Ni2 (C9H14N2O5)2·2H2O: monoclinic, space group P21/n, a = 1.1717(5), b = 0.9794(3), c = 1.2971(2) nm, β= 96.62(3), V= 1.4786(7) nm3, Dc = 1.377 g/cm3, Z = 2,μ=13.321 cm-1 (Mo-Kα), F(000)=640. The final R and Rw are 0.075 and 0.089 respectively. The Ni(Ⅱ) ion forms 2:2 complex with ligand. Two ligands are bridged by two Ni(Ⅱ) atoms which are bridged by two O atoms. Every Ni(Ⅱ) is coordinated by two N atoms and four 0 atoms. The coordination polyhedron of the Ni(Ⅱ) ion is a distorted octahedron.     

Synthesis and crystal structure of (E)-[(2-cyclohexenyl) vinyl]triaryltin

(E)-[(2-Cyclohexenyl)vinyl]triaryltin (aryl=phenyl, p-tolyl) were synthesized and characterized by elemental analysis, IR, 1H NMR spectroscopy. The crystal structure of (E)-[(2-cyclohexenyl)vinyl]triphenyltin was also determined by the X-ray diffraction. Experiments show that this compound has the conjugated system, which makes it have possible bioactivity and anti-tumor activity.     

Synthesis of functionalized pyrroles and fused pyrroles through intermolecular [3 + 2] cycloaddition reaction

A facile and efficient synthesis of pyrrole and pyrrole-fused heterocyclic compounds has been demonstrated. The current protocol involves the in situ generation of azomethine ylides which undergoes intermolecular cycloaddition reaction and subsequent treatment with DDQ provides the pyrrole and fused heterocyclic compounds in good yields.     

Synthesis and crystal structure of β-hexanitrohexaazaisowurtzitane

A polycyclic caged compound with high strain—hexanitrohexaazaisowurtzitane (HNIW)—has been synthesized via a three-step reaction: condensation, hydrogenolysis debenzylation and nitrolysis, starting with benzylamine and glyoxal. HNIW is the most powerful high energy density compound (HEDC) ever tested. β-HNIW possesses a caged structure consisting of two five-membered rings and one six-membered ring with a nitro group attached to each of the six bridging nitrogens. The nitro group lies basically within a plane. The lengths of C—C bonds of β-HNIW range from 0. 156 nm to 0.159 nm, 0.002–0.005 nm longer than the sp³ C-C bond. The β-HNIW’s crystal belongs to orthorhombic system and space groupPca2₁ with parameters:a = 0.9670 (2),b = 1.1616 (2),c = 1.3032 (3) nm;V = 1.4638(5) nm³,Z = 4; D_c = 1.989 g/cm³ and D_m = 1.982 g/cm³. Project supported by the Advanced Research Funds (12060451867) from the Commission of Science and Technology for National Defence.     

Synthesis,crystal structure and equilibrium studies on the novel bidentate amine adducts of bis[S-benzyl-β-N(p-nitrophenyl)methyldithiocarbazide]nickel(II)

The novel adducts [Ni(SN)2L] formed from chelating bidentate diamines and the square-planar bis[S-benzyl--N(p-nitrophenyl)methyldithiocarbazide]nickel(II) complex [Ni(SN)2] have been prepared and characterized. The bidentate diammines are 1,10-phenanthroline (phen), 2,2-bipyridine (bipy), 5-nitro-1,10-phenanthroline (NO2phen), 4,4-methyl-2,2-bipyridine(Mebipy) and 4,5-diazafluoren-9-one (diafo). The addition equilibrium constants, K, determined by u.v.-vis. spectrophotometry in CH2Cl2, were influenced by the coordinating ability of the added ligands in the order: Kphen >; KNO2phen >; Kdiafo; and KMebipy >; Kbipy >; Kdiafo. The structure of the phenanthroline adduct was determined in order to study the mechanism of the addition processes and the [Ni(SN)2phen] complex has been characterized by X-ray crystal structure analysis. The coordination geometry of the nickel atom is distorted octahedral. The four nitrogen atoms of the two SN ligands and the phenanthroline form an equatorial plane with a Ni-N distance of ca. 2.10 AÅ, and the two sulfur atoms are located at the axial position with an average Ni-S distance of 2.40 AÅ. From the results of the structural determination and the addition equilibrium studies, a possible addition mechanism is also discussed.     

Synthesis,crystal structure and Raman spectra of [dabcoH2]CuICl3, [dabcoH2]3Cl4CuIICl4(DMSO) and Cu3Cl3(dabco)(DMSO) (dabco = 1,4-diazabicyclo [2.2.2] octane)

Dissolving elemental copper in a CCl₄–DMSO mixture in the presence of dabco (dabco = 1,4-diazabicyclo [2.2.2] octane) resulted in the formation of a compound with the composition [dabcoH₂][CuCl₃] featuring a univalent copper salt. This compound, composed of discrete dabcoH₂²⁺ cations and CuCl₃^2? anions, represents the first example of a copper(I) chloride derivative containing a doubly protonated [dabcoH₂]²⁺ unit, and a very rare example of the oxidative dissolving of copper in a CCl₄–DMSO mixture to give a Cu(I) compound. The addition of some drops of water to the initial reaction mixture led to the formation of the [dabcoH₂]₃Cl₄CuCl₄(DMSO). Three [dabcoH₂]²⁺ units and four Cl^? anions, bound via N–H…Cl hydrogen bonds, form a horseshoe-like cationic fragment. The divalent copper ion possesses a rather unusual pseudo-tetrahedral surrounding. The comproportionation reaction of CuCl₂·2H₂O and copper powder in the presence of dabco in DMSO results in the formation of the Cu₃Cl₃(dabco)(DMSO) complex. Copper and chlorine ions form unprecedented Cu₆Cl₆ cores, interconnected by neutral dabco linkers into infinite 2-D layers. All the compounds were characterized using the single-crystal X-ray diffraction technique and Raman spectroscopy.     

Synthesis, crystal structure, EPR spectra of Cu2+ doped [Zn(methylisonicotinate)2(H2O)4]·(sac)2 single crystal

The tetraaquabis(methylisonicotinate)zinc(II) disaccharinate [hereafter, [Zn(mein)2(H2O)4]·(sac)2], complex has been synthesized and characterized by spectroscopic IR, EPR and X-ray diffraction technique. The octahedral Zn(II) ion, which rides on a crystallographic centre of symmetry, is coordinated by two monodentate mein ligands through the ring nitrogen and four aqua ligands to form discrete [Zn(mein)2(H2O)4] unit, which captures two saccharinate ions in up and down positions, each through intermolecular hydrogen bonds. The magnetic environments of Cu2+ doped [Zn(mein)2(H2O)4]·(sac)2 complex have been identified by electron paramagnetic resonance (EPR) technique. EPR spectra of Cu2+ doped [Zn(mein)2(H2O)4]·(sac)2 single crystals have been studied between 113 and 300 K in three mutually perpendicular planes. The calculated results of the Cu2+ doped [Zn(mein)2(H2O)4]·(sac)2 indicate that Cu2+ ion contains two different complexes and each complexes are located in different chemical environments and each environment contains two magnetically inequivalent Cu2+ sites in distinct orientations occupying substitutional positions in the lattice. The vibrational spectra of this compound were discussed in relation to other compounds containing methyl isonicotinate and saccharinate complexes. The assignments of the observed bands were discussed.     

Synthesis,crystal structure,thermal decomposition,and explosive properties of [Bi(tza)3] n (tza = tetrazole acetic acid)

A coordination compound based on tetrazole acetic acid (Htza) and bismuth(III), [Bi(tza)₃] _n , was synthesized and characterized by single crystal X-ray diffraction analysis, elemental analysis, FT-IR, and ¹H NMR spectroscopy. The crystallographic data show that the crystal belongs to monoclinic, P2₁/n space group, a?=?0.91968(19)?nm, b?=?0.94869(19)?nm, c?=?1.7824(4)?nm, β?=?101.488(3)°, and Z?=?4. The central bismuth(III) is nine-coordinate by three nitrogens from three tetrazole rings and six oxygens of the carboxylate of another three tza^? ions, with each tza^? tridentate, chelating, bridging coordination. The coordination bonds and the intramolecular hydrogen bonds make the complex pack into a layered structure in polymer form. The thermal decomposition mechanism of the title complex was investigated by DSC and TG-DTG techniques. Under nitrogen at a heating rate of 10°C?min^?1, thermal decomposition of the complex contains two intense exothermic processes between 217.4°C and 530.3°C in the DSC curve; the final decomposed residue at 570°C was Bi₂O₃. Sensitivity tests showed that [Bi(tza)₃] _n was sensitive to impact and flame stimulus.     

Synthesis of Calix[4]pyrroles: A Class of New Molecular Receptor

RecentlySesslerandco-workersdiscoveredthatthemeso-octaalkylporphyrinogensshowedinterestinganionandneutralsubstratebindingpropertiesandmightserveasaclassofneweasy-to-makemolecularreceptorintheareaofsupramolecularchemistry'.However,themeso-octaalkylpor...