Synthesis and Crystal Structure of [2-Hydroxy- 5-（4-hydroxy-3-phenyliminomethylbenzyl）-benzylidene]-phenyl-amine

The title compound [2-hydroxy-5-（4-hydroxy-3-phenyliminomethyl-benzyl）-benzylidene]-phenyl-amine （C27H22N2O2, Mr = 406.47） was synthesized by 5,5′-methylene-bissalicylal- dehyde with aminobenezene, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group C2/c with a = 4.4026（6）, b = 1.501（13）, c = 0.95818（12） nm, β = 90.868（2）°, V= 4.2813（9） nm^3, Z= 8, Dc= 1.292 g/cm^3,μ = 0.010, F（000） = 1744, R = 0.0576 and wR = 0.1450 for 3766 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that the molecule has a pair of intramolecular OH…N hydrogen bonds.     

Synthesis,Crystal Structure and Biological Activity of 25,27-Di(α,γ-diketo-p-methylphenylbutoxy)-26,28-dihydroxy p-tert-butylcalix[4]arene

The title complex(C66H76O8·CH3CN) was synthesized and structurally determined by single-crystal X-ray diffraction method. It crystallizes in monoclinic, space group P21/c with a = 22.384(13), b = 13.413(7), c = 21.867(12), β = 112.257(7)°, C68H78NO8, Mr = 1037.31, Dc = 1.133 g/cm3, V = 6076(6) 3, Z = 4, F(000) = 2224, μ(MoKa) = 0.073 mm-1, T = 296(2) K, 10276 independent reflections with 5469 observed ones(I 2σ(I)), R = 0.0797 and wR = 0.2316 with GOF = 1.027(R = 0.1442 and wR = 0.2689 for all data). The calixarene moiety maintains the symmetric cone conformation through intramolecular O–H···O hydrogen bonds. The inhibition of the strand transfer process of HIV-1 integrase of the title compound was also evaluated. Preliminary bioassays indicated that it has a low inhibition ratio(24.85%) at the concentration of 50 μM.     

Synthesis and crystal structure of 15α,20α-di(4-hydroxylphenyl)calix[4]pyrroles and 10α,20β-di(4-hydroxylphenyl)calix[4]pyrroles

In the presence of methanesulfonic acid as catalyst, the condensation reactions of 5,5′-dialkyldipyrromethanes with p-hydroxyacetophenone in methanol resulted in a mixture of the unexpected polysubstituted 15α,20α-di(4-hydroxylphenyl)calix[4]pyrroles and the expected 10α,20β-di(4-hydroxylphenyl)calix[4]pyrroles in comparable lower yields. The crystal structures of the new calix[4]pyrroles and their oxyacetate derivatives were successfully determined by X-ray diffraction and the intermolecular interactions in the solid state is briefly discussed.     

Synthesis, Crystal Structure and Properties of 2,7-Bis [4-（diphenylamino）phenyl] fluorene

A novel fluorene derivative containing triphenylamine groups, 2,7-bis[4-(diphenylamino)-phenyl]fluorene (C49H36N2 , Mr= 652.80), was synthesized via Suzuki coupling reaction (yield: 19%) and its crystal structure was determined by single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 9.320(4), b = 11.250(6), c = 17.369(6) , α = 88.035(3), β = 86.450(5), γ = 73.524(5)°, V = 1742.8(13) 3 , Z = 2, Dc = 1.244 g/cm 3 , μ(MoKα) = 0.072 mm -1 , F(000) = 688, S = 1.095, the final R = 0.0616 and wR = 0.1878. It presents a linear framework constituted by a linkage of fluorene as a bridge and two triphenylamine groups. Its spectral and electrochemical properties were studied by UV-Vis absorption, fluorescence spectroscopy and cyclic voltammetry (CV). This compound can emit intense blue fluorescence with a peak wavelength of 446 nm and a full width at half maximum (FWHM) of 38 nm under UV excitation at 350 nm in film. The highest occupied molecular orbital (HOMO) energy level, the lowest unoccupied molecular orbital (LUMO) energy level and optical band gap (Eg) of the title compound are -5.46, -2.57 and 2.89 eV, respectively.     

Synthesis,Crystal Structure and Recognition Properties of 2-（5-（4-Chlorophenyl）-1-phenyl-4,5-dihydro-1H-pyrazol-3-yl）pyridine

The title compound 2-(5-(4-chlorophenyl)-1-phenyl-4,5-dihydro-1H-pyrazol-3-yl)- pyridine(C20H16ClN3, Mr = 333.81) has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/n with a = 10.9925(12), b = 11.0378(12), c = 14.2751(18) , β = 98.074(11)°, V = 1714.9(3)3, Z = 4, Dc = 1.293 g/cm3, μ(MoKα) = 0.228 mm-1, F(000) = 696, the final R = 0.0521 and wR = 0.1349 for 3495 observed reflections with I 2σ(I). Intermolecular C–H...π interactions and π-π stacking interactions stabilize the crystal structure. The binding study by fluorescence spectroscope titration showed that the title compound can selectively recognize Fe3+ in THF solution with fluorescence quenching.     

Synthesis,Bioactivity and Crystal Structure Analysis of Diisopropyl[（4-cyanopyrazol-3-ylamino）（2-hydroxyl-phenyl） methyl]phosphonate

The title compound,diisopropyl[(4-cyanopyrazol-3-ylamino)(2-hydroxylphenyl) -methyl] phosphonate was synthesized by the addition reaction of diisopropyl phosphite and N-(4-cyanopyrazole-3-yl) -2-hydroxylphenyl-imine. Its structure was characterized by IR,1H NMR,elemental analysis and single-crystal X-ray diffraction. The crystal belongs to the triclinic system,space group P1 with a = 9.1840(13) ,b = 9.2278(13),c = 12.1952(17) ,α = 93.846(2) ,β = 90.947(2) ,γ = 111.289(2) °,V = 959.9(3) 3,Dc = 1.309 g/cm3,Z = 2,μ(MoKa) = 0.173,F(000) = 400,the final R = 0.0414 and wR = 0.1196 for 2985 observed reflections(I > 2σ(I)) . The pyrazole and benzene moieties are approximately coplanar in each case. The dihedral angle between planes 1 and 2 is 82.99°. The crystal structure is stabilized by three intermolecular hydrogen bonds of O(1) -H(1) …O(2) ,N(2) -H(2) …N(3) and N(2) -H(2) …O(1) . Preliminary bioassay indicated that the title compound possessed antiviral activity to some extent.     

Synthesis and Crystal Structure of N-phenyl-N-[（o-nitrophenylacetyl）oxy]benzamide

The compound N-phenyl-N-[（o-nitrophenylacetyl）oxy]benzamide （C21HI6N2Os, Mr = 376） has been synthesized by the reaction of N-hydroxy-N-phenylbenzamide with 2-（2-nitro- phenyl）acetyl chloride in dichlorom-ethane and its structure Was characterized by 1H NMR, 13C NMR, IR, H RMS（ESI） and single-crystal X-ray diffraction. The crystal of the title compound belongs to monoclinic, space group C2/c with a = 32.30（2）, b = 8.400（5）, c = 15.099（9） A, fl = 114.256（10）°, V = 3735（4） A3, Z = 8, D, = 1.339 g/cm3, F（000） = 1568, p = 0.097 mm-1, the final R = 0.0506 and wR = 0.1176 for 2318 observed reflections （1 〉 2a（/））. The title molecule contains three branched chains with its center placed at the midpoint of N. The phenyl ring （C（1）＇-C（6）） makes a dihedral angle of 70.3（1）° with the phenyl ring （C（10）-C（15）） of benzoyl group, and 14.3（1）° with the phenyl ring （C（16） - C（21））, Hydrogen bonds C（5）-H（5）...O（1） and C（12）-H（12）...O（3） together with it-Jr stacking interactions contribute to the stability of the structure.     

Synthesis and Luminescent Properties of Cationic Ir（Ⅲ） Complexes of 2-Phenylquinoline Derivatives

Two cationic iridium(III) complexes, [(pqcm)2Ir(pybz)](PF6) (Ir1) and [(pqcm)2Ir(apybz)](PF6) (Ir2) (pqcmH=2-phenyl-quinoline-4-carboxylic acid methyl ester, pybz=2-pyridyl-benzimidazole, apybz=1-allyl-2-pyridyl-benzimidazole), were readily synthesized from the reaction of IrIII-μ-chloro-bridged dimer [Ir(pqcm)2(Cl)]2 and corresponding ancillary ligands, and characterized by NMR and mass spectroscopies. The structure of Ir2 was also confirmed by single-crystal X-ray diffraction. The photophysical properties of the two complexes were also investigated. Ir1 shows deep red emission peaked at around 652 nm with the phosphorescence quantum yield of ca. 0.29 and the emission lifetime of 233 ns, while Ir2 shows red emission peaked at around 615 nm with the phosphorescence quantum yield of ca. 0.13 and the emission lifetime of 430 ns. The active hydrogen on pybz ligand is believed to have a great influence on the photophysical properties of Ir1.     

Synthesis,Structure and Properties of Two New Coordination Polymers Based on 4-[（8-Hydroxy-5-quinolinyl）azo]-benzenesulfonic Acid

Two new coordination polymers based on 4-[（8-hydroxy-5-quinolinyl）azo]-benzenesulfonic acid（H2L）,{[CdL（H2O）2]·H2O}n（1） and {[CdL（en）]·EtOH}n（2）（en=ethylenediamine）,were solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Compounds 1 and 2 exhibit infinite 1D ladder-shaped chain structures,which are isostructural except that the two coordinating water molecules in compound 1 were replaced by one en molecule in compound 2 due to the use of different organic base.Compounds 1 and 2 were constructed into different supramolecular frameworks by hydrogen bonding and π…π stacking interactions.In addition,the fluorescent properties of compounds 1 and 2 were investigated.Furthermore,they were also investigated via IR spectral analysis,elemental analysis,powder X-ray diffraction（PXRD） and thermogravimetric analysis（TGA）.     

Synthesis and Crystal Structure of 2-（ 4-Decarboxydehydroabietyl）- 5-p-tolyl-[ 1,3,4 ]-oxadiazole

2-（4-Decarboxydehydroabietyl）-5-p-toyl-[1,3,4]-oxadiazole, C28H34N2O, has been synthesized and characterized by IR, NMR, elemental analysis and single-crystal X-ray diffraction method. The crystal belongs to the orthorhombic system, space group P212121 with a = 6.1351（5）, b = 14.8495（19）, c = 25.9050（2） A, V = 2360.0（4） A3, Z = 4, Mr = 414.57, Dc = 1.167 Mg/m^3, 2 = 0.71073 A,μ（MoKa） = 0.070 mm^-1, F（000） = 896, the final R = 0.0452 and wR = 0.1076 for 1647 observed reflections with I 〉 2σ（I）. There are five rings in the crystal structure of the title compound, but the oxadiazole ring is non-coplanar with the benzene ring D.     

Synthesis and crystal structure of Ni,Cu complexes of 5-methyl-10,10,15,15,20,20-hexaethylcalix[4]pyrrole mono-Schiff bases

The functionalized calix[4]pyrrole meso-substituted Schiff bases were conveniently prepared by fourstep synthetic route. Furthermore, the nickel and copper complexes of calix[4]pyrrolemeso-substituted Schiff base with 1:2 stoichiometry were obtained. The crystal structures of the calix[4]pyrroles and their metal complexes were determined by X-ray diffraction.     

Squaramide-substituted calix[4]pyrrole: Synthesis and ion binding studies

Squaramide-substituted calix[4]pyrrole 2 was synthesized and its anion-binding properties were investigated. On the basis of UV spectroscopy, ¹H NMR spectroscopic and computational DFT model analyses, compared with the parent calix[4]pyrrole 1, compound 2 shows significantly enhanced binding affinities for anions in CH₂Cl₂, and it was concluded that this increase in affinity is ascribed to participation of the squaramide unit in anion binding.     

Mono Halogen Substituted Calix[4]pyrroles: Fine-tuning the Anion Binding Properties of Calix[4]pyrrole

Abstract

Single halogen atom (i. e. I, Br, Cl and F) substituted calix[4]pyrroles, compounds 2, 3, 4 and 5, were synthesized. Studies of these systems reveal that replacement of a single β-pyrrolic hydrogen atom can increase the anion binding ability of calix[4]pyrroles for a variety of anions (e. g. Cl^?, Br^?, H₂PO₄ ^? and HSO^? ₄) relative to normal non-halogen substituted calix[4]pyrrole 1. In the case of chloride anion, the expected relative affinity sequence of 5 > 4 > 3 > 2 was observed. This was not found to be true for Br^?, H²PO^? ₄, and HSO^? ₄. Here, the chlorine substituted calix[4]pyrrole 4 was found to display a slightly higher affinity in the case of each anion than the fluorine-bearing derivative 5. This was rationalized in terms of intermolecular NH … F hydrogen bonding interactions being present in CD₂Cl₂ solutions of 5. Support for this latter conclusion came from concentration and temperature-dependent NMR spectroscopic studies.

A matched set of mono halogen substituted calix[4]pyrroles was used to study in detail, the extent to which halogen substituents may be used to fine-tune the anion binding properties of calix[4]pyrroles.     

Synthesis of Calix[4]resorcinarene Schiff Bases

Introduction Calix[4]resorcinarenes are cyclic tetramers in which four resorcinol units are linked via alkylmethylene bridges in the o-position to each resorcinic hydroxyl group[1]. Their structures resemble that of p-butylcalix[n]arenes and render them of interest as host compounds in many contemporary fields of supramolecular chemistry.     

New redox anion receptors based on calix[4]pyrrole bearing ferrocene amide

Two redox anion receptors based on calix[4]pyrrole and ferrocene have been synthesized. The electrochemical investigation revealed that these compounds can be response to the anions with different shifts of Fc/Fc⁺ couple. With the ¹H NMR titration study, the selectivity to F⁻ and AcO⁻ ions in CD₃CN solution was confirmed. The conformations of the mono-aromatic meso-substituted calix[4]pyrroles, which were the synthetical intermediate of the ferrocene based receptors, and their anion complexes in the solid state have also been studied by single X-ray crystallography, and the rationality of the crystal conformations was proved by theoretical study.     

Effect of fluorine substitution in calix[4]pyrrole: A DFT study

Using density functional theory we investigate the ground-state geometries and electronic structures of calix[4]pyrrole (C4P) and its fluorine analogue (F-C4P). The HOMO–LUMO energy gap of C4P is 5.9 eV and remains nearly the same upon H-by-F replacement (5.7 eV). Fluorine substitution increases both the vertical and adiabatic ionization potentials of C4P by 0.8 eV while the electron affinity of either macrocycle is negative thus indicating that the corresponding radical anion in the gas-phase is thermodynamically unstable. It is shown that the topology of the LUMOs of both C4P and F-C4P have important implications for the spherical recognition of halide anions. The simulated IR, NMR, and electronic spectra display important fingerprints for the characterization of these macrocycles.     

Synthesis, characterization and photochromic studies of three novel calix[4]arene-Schiff bases

Synthesis and characterization of three novel Schiff bases based on calix[4]arene are described. The synthesis of these compounds had been achieved by the condensation of salicylaldehyde derivatives with the amine group of upper rim of de-butylcalix[4]arene in ethanol. The structures of new compounds were confirmed on the basis of IR, (1)H NMR, (13)C NMR, MS and elementary analysis. Photochromic properties of compounds were studied in CH(3)CN by UV/vis and fluorescence spectra. These Schiff base-calix[4]arene can be used in certain 'supermolecular electronic devices' through combining the photochromic behaviors with others such as non-linear optical or charge transfer properties.     

Synthesis and self-assembly of novel calix[4]arenocrowns: formation of calix[4]areno[2]catenanes

A series of novel calix[4]arenocrowns 1a-c were efficiently synthesized by a one-pot reaction of calix[4]monohydroquinone diacetate 5 with ditosylate 6 and its analogues in the presence of sodium hydroxide. It was found that the calix[4]arenocrowns could form stable pseudorotaxane-type complexes 2a-c with paraquat, and further self-assemble into calix[4]areno[2]catenanes 3a-c with dicationic salt 8 and p-bis(bromomethyl)benzene.     

杯[4]间苯二酚芳烃Schiff碱衍生物的合成及其离子萃取性能

通过控制条件,使两种乙氧基羰基甲氧基杯[4]间苯二酚芳烃2a和2b的酯基与1,6-己二胺的一个氨基反应形成酰胺3a和3b,剩余的一个氨基再与水杨醛反应,得到了相应的杯芳烃Schiff碱衍生物4a和4b,对其进行了金属离子的液-液萃取性能研究.结果表明,Schiff碱基团的引入能大大增强杯芳烃与金属离子的配位能力,而杯芳烃空腔的存在又能提高Schiff碱与金属离子的配位选择性.